JPH04209605A - Improved process for production of chlorinated polyolefin - Google Patents
Improved process for production of chlorinated polyolefinInfo
- Publication number
- JPH04209605A JPH04209605A JP34084190A JP34084190A JPH04209605A JP H04209605 A JPH04209605 A JP H04209605A JP 34084190 A JP34084190 A JP 34084190A JP 34084190 A JP34084190 A JP 34084190A JP H04209605 A JPH04209605 A JP H04209605A
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin
- reaction
- chlorinated
- chlorination
- hydrochloric acid
- 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.)
- Granted
Links
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 48
- -1 acrylic ester Chemical class 0.000 claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000004711 α-olefin Substances 0.000 claims abstract description 7
- 229920001519 homopolymer Polymers 0.000 claims abstract description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 34
- 238000005660 chlorination reaction Methods 0.000 abstract description 31
- 229920000058 polyacrylate Polymers 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 11
- 238000009736 wetting Methods 0.000 abstract description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 20
- 230000000903 blocking effect Effects 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は改良された塩素化ポリオレフィンの製造法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an improved method for producing chlorinated polyolefins.
(従来の技術)
現在塩素化ポリオレフィンの製造法は、気相塩素化法、
溶媒中での塩素化法、水性懸濁下での塩素化法が報告さ
れている。気相塩素化法は製品の熱安定性2着色、用途
限定等の理由により一般的な方法となっていない。(Prior technology) Currently, the methods for producing chlorinated polyolefins include gas phase chlorination method,
A chlorination method in a solvent and a chlorination method in an aqueous suspension have been reported. The gas phase chlorination method is not a common method due to reasons such as the thermal stability of the product, the coloring, and the limited use.
溶媒中での塩素化法は、四塩化炭素を主体とする不活性
塩素系溶媒中で塩素化するので、比較的均一な塩素化ポ
リオレフィンが得られるが、低沸・点溶媒を使用し、高
温で反応するため高分子量物を塩素化するには反応系が
高粘度になり、ポリオレフィンを溶解して反応するため
、高分子量物を塩素化するには反応系が高粘度になり、
ポリオレフィン濃度の低いところで反応しなければなら
ないという欠点がある。この方法は塗料、接着剤等に使
用される溶媒可溶型の比較的低分子量塩素化ポリオレフ
ィンの製造に実施されている。また四塩化炭素は今後大
気汚染の問題よりその使用はますます困難になってきて
いる。In the chlorination method in a solvent, relatively uniform chlorinated polyolefin can be obtained because chlorination is carried out in an inert chlorine-based solvent mainly composed of carbon tetrachloride. In order to chlorinate a high molecular weight substance, the reaction system becomes highly viscous, and the reaction system dissolves the polyolefin.
The drawback is that the reaction must be carried out at low polyolefin concentrations. This method is used to produce solvent-soluble relatively low molecular weight chlorinated polyolefins used in paints, adhesives, and the like. Furthermore, it is becoming increasingly difficult to use carbon tetrachloride due to air pollution problems.
一方水性懸濁下での塩素化反応を行うことが望ましいが
、これが原因となって反応中のポリオレフィン粒子のブ
ロッキング現象につながる。On the other hand, it is desirable to carry out the chlorination reaction under aqueous suspension, which leads to a blocking phenomenon of the polyolefin particles during the reaction.
この防止策として各種分散剤を使用する試みが数多く報
告されている。例えばポリビニルアルコール、ポリアク
リル酸、無水マレイン酸とメチルビニルエーテルもしく
はスチレンとの共重合物。Many attempts to use various dispersants have been reported as a preventive measure against this problem. For example, copolymers of polyvinyl alcohol, polyacrylic acid, maleic anhydride and methyl vinyl ether or styrene.
ポリアクリルアミド、ポリビニルピロリドン等を用いる
(特公昭、i6−21729号、特公昭47−7896
号。Using polyacrylamide, polyvinylpyrrolidone, etc.
issue.
特開昭54−124096号等)。また界面活性剤を添
加する例もある。現在報告されている方法ではこれらの
分散剤や界面活性剤を水に分散させてからポリオレフィ
ンを分散させているため、反応の初期撹拌によって泡立
ちが多くポリオレフィン粒子は軽く水濡れ性が悪いため
反応容器の上層部に多量に浮遊する。そのため反応槽内
の気−液界面の気゛ 相壁部に帯状に付着されながら塩
素化され、ブロッキング物が途中脱離、付着をくり返さ
れる。またポリオレフィン粒子の水濡れ性が悪いため、
初期に不均一な粒子が残りそのまま塩素化されると反応
生成物中に過塩素化物や粗大粒子として含まれてくる。JP-A-54-124096, etc.). There are also examples of adding surfactants. In the currently reported method, these dispersants and surfactants are dispersed in water and then the polyolefin is dispersed, which results in a lot of foaming due to initial stirring of the reaction, and the polyolefin particles are light and have poor water wettability, so the reaction vessel Floating in large quantities in the upper layer of the water. Therefore, it is chlorinated while being attached to the gas phase wall at the gas-liquid interface in the reaction tank in a band-like manner, and blocking substances are repeatedly desorbed and attached during the process. In addition, due to the poor water wettability of polyolefin particles,
If non-uniform particles remain in the initial stage and are chlorinated as they are, they will be included in the reaction product as perchlorinated products or coarse particles.
これらは反応終了後、副生塩酸の中和時にブロッキング
粒子過塩素化物粒子内部に入り込んだ@酸や添加剤の中
和洗浄が十分に行えない原因となり、塩素化ポリオレフ
ィンの着色や熱安定性低下につながる。これらの問題は
今なお十分に解決されたと言えず、現在はブロッキング
防止のため原料ポリオレフィンの融点より数十度低い温
度で塩素化を行ったり途中塩素化を中止してポリオレフ
ィン融点まで温度を上げ(アニール)、また温度を下げ
て再び塩素化するような手段が報告されている。After the reaction is complete, the blocking particles and the additives that have entered the inside of the perchlorinated particles during the neutralization of the by-product hydrochloric acid cannot be sufficiently neutralized and washed, resulting in coloration of the chlorinated polyolefin and a decrease in thermal stability. Leads to. These problems have not yet been fully resolved, and currently, in order to prevent blocking, chlorination is carried out at a temperature several tens of degrees lower than the melting point of the raw polyolefin, or chlorination is stopped midway through and the temperature is raised to the melting point of the polyolefin ( (annealing), and methods of lowering the temperature and chlorinating again have been reported.
他に二酸化チタン、カーボンブラック、タルク。Other ingredients include titanium dioxide, carbon black, and talc.
シリカ、ポリ塩化どニール等の無機系又は有機系の微粉
末を用いて塩素化時のブロッキングを防止する方法も報
告されているが、反応生成物中にこれらの添加剤が多量
に残り製品の使用上の規制を受け、実用的な方法とは言
えない。Methods to prevent blocking during chlorination using inorganic or organic fine powders such as silica and polychlorinated polychloride have also been reported, but a large amount of these additives remains in the reaction product and may cause problems in the product. It cannot be said to be a practical method as it is subject to usage regulations.
一般に水性懸濁法によって得られた塩素化ポリオレフィ
ンは比較的分子量か大きく数万〜数10万。In general, chlorinated polyolefins obtained by the aqueous suspension method have relatively large molecular weights, ranging from tens of thousands to hundreds of thousands.
塩素含量20〜50重量%でゴム状からプラスチック状
の性能を有するものまで多岐にわたって生産されている
。A wide variety of materials are produced, ranging from rubber-like to plastic-like properties with a chlorine content of 20 to 50% by weight.
これらの用途はポリエチレン、ポリプロピレン。These applications include polyethylene and polypropylene.
ポリ塩化ビニール、ABS樹脂等のポリマーブレンド用
又は塩素化ポリオレフィン単独で成形品。Molded products for polymer blends such as polyvinyl chloride and ABS resin, or chlorinated polyolefin alone.
架橋せしめてゴム状成形品等へ利用されており、塩素化
ポリオレフィンとしては、できるだけ均一に塩素化され
細かい粒子状で熱安定性に優れているものが望まれる。It is crosslinked and used for rubber-like molded products, etc., and the desired chlorinated polyolefin is one that is chlorinated as uniformly as possible, has a fine particle shape, and has excellent thermal stability.
(発明が解決しようとする課題)
本発明は以上の点にかんがみポリオレフィンを水性懸濁
法により塩素化するに際し、ポリオレフィン粒子のブロ
ッキングを防止し、均一な塩素化と高温反応により熱安
定性に優れた塩素化ポリオレフィンを得る方法を提供す
ることを目的とする。(Problems to be Solved by the Invention) In view of the above points, the present invention prevents blocking of polyolefin particles when chlorinating polyolefin by an aqueous suspension method, and achieves excellent thermal stability through uniform chlorination and high temperature reaction. The object of the present invention is to provide a method for obtaining a chlorinated polyolefin.
(課題を解決するための手段)
本発明はすなわち、水性懸濁法によりポリオレフィンを
塩素化するに際し、原料液として粉末状ポリオレフィン
を予め水溶性アクリル系重合体−界面活性剤混合液で湿
潤処理し塩酸水溶液中に分散せしめたスラリー液を使用
することを特徴とする改良された塩素化ポリオレフィン
の製造法である。(Means for Solving the Problems) In other words, when polyolefin is chlorinated by an aqueous suspension method, the present invention wets a powdered polyolefin as a raw material solution with a water-soluble acrylic polymer-surfactant mixture in advance. This is an improved method for producing chlorinated polyolefin, characterized by using a slurry liquid dispersed in an aqueous hydrochloric acid solution.
本発明に用いられるポリオレフィンとは、粉末状のα−
オレフィンの単独重合体又は共重合体で例えばポリエチ
レン、ポリプロピレン、エチレン−プロピレン共重合体
、エチレン−ブテン共重合体、プロピレン−ブテン共重
合体、エチレン−アクリル酸エステル共重合体、エチレ
ン−酢酸ビニール共重合体、エチレン−ブタジェン共重
合体等の結晶構造を有する重合体という。特にポリエチ
レン、エチレン−ブテン共重合体、エチレン−アクリル
酸エステルもしくは酢酸ビニール共重合体等が適当でお
る。The polyolefin used in the present invention is a powdered α-
Olefin homopolymers or copolymers, such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, propylene-butene copolymer, ethylene-acrylic acid ester copolymer, ethylene-vinyl acetate copolymer It refers to a polymer having a crystal structure such as a polymer or an ethylene-butadiene copolymer. Particularly suitable are polyethylene, ethylene-butene copolymers, ethylene-acrylic esters or vinyl acetate copolymers.
ポリオレフィンの分子銀としては、通常io、oo。The molecular silver for polyolefins is usually io or oo.
〜1,000,000好ましくは40.000〜300
.000のものが適当である。ポリオレフィンの粒度は
特に制限はないが不均一系の塩素化反応であるため、均
一な塩素化物@得るにはできるだけ細かい方が好ましい
。通常50〜1000taの粒子が適当である。~1,000,000 preferably 40,000-300
.. 000 is appropriate. There is no particular limit to the particle size of the polyolefin, but since the chlorination reaction is a heterogeneous one, it is preferable to make it as fine as possible in order to obtain a uniform chlorinated product. Particles of 50 to 1000 ta are usually suitable.
本発明において用いられる水溶性アクリル系重合体とは
アクリル酸もしくはアクリル酸エステルの重合体もしく
はこれらの共重合体7又はこれらの重合体もしくは共重
合体のアルカリ金属塩もしくはアンモニウム塩で分子量
3000以上のもので特に10.000以上のものが好
ましい。上記アクリル酸エステルとしては炭素数1〜4
のアルキルエステルが好ましい。これら重合体のうち、
水可溶又はコロイダルディスバージョンとなり得るもの
が本発明に適する。The water-soluble acrylic polymer used in the present invention is a polymer of acrylic acid or acrylic ester, or a copolymer thereof, or an alkali metal salt or ammonium salt of these polymers or copolymers, and has a molecular weight of 3000 or more. In particular, those with a value of 10,000 or more are preferred. The above acrylic ester has 1 to 4 carbon atoms.
Alkyl esters of are preferred. Among these polymers,
Those capable of water soluble or colloidal dispersion are suitable for the present invention.
界面活性剤としては、非イオン活性剤又はアニオン活性
剤、例えばポリオキシエチレンアルキルエーテル類、ポ
リオキシアルキルフェノールヱステル類、ポリオキシエ
チレンアルキルエステル類。Surfactants include nonionic or anionic surfactants, such as polyoxyethylene alkyl ethers, polyoxyalkylphenol esters, and polyoxyethylene alkyl esters.
ソルビタンアルキルエステル類、エチレンオキサイド−
プロピレンオキサイドブロックポリマー等の非イオン活
性剤、アルキルベンゼンスルホン酸ソーダ、アルコール
硫酸エステル、アルキルスルホン酸、アルキルアリルス
ルホン酸又はそれらのナトリウム塩等のアニオン活性剤
が適している。Sorbitan alkyl esters, ethylene oxide
Nonionic activators such as propylene oxide block polymers, anionic activators such as sodium alkylbenzenesulfonates, alcohol sulfates, alkylsulfonic acids, alkylarylsulfonic acids or their sodium salts are suitable.
またアニオン活性スチレン系重合体の添加も効果がある
。Addition of an anion-active styrenic polymer is also effective.
現在報告、実施されている水性懸濁法による塩素化に従
うと、まず水に分散剤、界面活性剤を溶解させておき、
その中に粉末状ポリオレフィンを分散させて塩素化反応
を行うが、ポリオレフィン粒子が軽量で水濡れ性が悪い
ことにより、ポリオレフィン粒子が浮遊したり、反応器
の上層部に多く集まり、容器の気−液界面の気相部分に
帯状に付着し、分散性も悪くなる。これらが原因となっ
て反応中のブロッキングにつながり、反応生成物中に不
均一塩素化物や過塩素化物が混入してくる。According to the currently reported and practiced aqueous suspension method for chlorination, a dispersant and a surfactant are first dissolved in water.
Powdered polyolefin is dispersed in the reactor to carry out the chlorination reaction, but because the polyolefin particles are lightweight and have poor water wettability, the polyolefin particles tend to float or collect in the upper layer of the reactor, causing the air in the container to evaporate. It adheres in a band shape to the gas phase portion of the liquid interface, resulting in poor dispersibility. These factors lead to blocking during the reaction, and heterogeneous chlorination and perchlorination are mixed into the reaction product.
また塩素化反応進行とともに副生塩酸によって系は塩酸
酸性となり特にアクリル系重合物は析出し粒子となって
系全体に分散してくるため、ポリオレフィン粒子にはブ
ロッキング防止剤として十分な効果を得ようとすると大
量に必要となる。−方界面活性剤とアニオン活性スチレ
ン重合体は、系が塩酸酸性になっても均一に分散してい
るが、反応の進行とともに副生塩酸や次亜塩素酸の作用
を受けて分散能力が低下してくる。このため界面活性剤
の使用量を増したり、反応途中で添加する方法がとられ
るが、かえって反応系の泡立ちか大きくなり、前)ホの
理由により好ましくない。In addition, as the chlorination reaction progresses, the system becomes acidic due to the by-product hydrochloric acid, and the acrylic polymer in particular becomes precipitated particles and disperses throughout the system, so polyolefin particles may have sufficient effect as an anti-blocking agent. Therefore, a large amount is required. - The surfactant and anionically activated styrene polymer are uniformly dispersed even when the system becomes acidic with hydrochloric acid, but as the reaction progresses, the dispersion ability decreases due to the action of by-product hydrochloric acid and hypochlorous acid. I'll come. For this reason, the amount of surfactant used is increased or the surfactant is added during the reaction, but this results in increased foaming of the reaction system, which is not preferable for the reason mentioned above.
本発明者らは上記アクリル系重合体が水系では完全に溶
解するが、塩酸水溶液系では不溶性で析出することや、
ポリオレフィンの水濡れ性改良に効果があること、さら
にアクリル系重合体が塩素化されてもアルカリによる中
和洗浄工程で溶解除去できることに看目し詳細な検討を
行った。その結果、粉末状ポリオレフィンを水溶性アク
リル系重合体−界面活性剤混合液で予め湿潤処理し、こ
れを1〜30重量%塩酸水溶液中に分散することにより
、アクリル系重合体が効率よくポリオレフィン表面に定
着せしめることができ、界面活性剤は塩酸水溶液に溶解
しポリオレフィン粒子の分散を助ける働きをし、濡れ性
1分散性の良好なポリオレフィンの塩酸スラリー液を得
ることができた。The present inventors discovered that the above acrylic polymer completely dissolves in an aqueous system, but is insoluble and precipitates in an aqueous hydrochloric acid solution system.
A detailed study was conducted based on the fact that this method is effective in improving the water wettability of polyolefins, and that even if the acrylic polymer is chlorinated, it can be dissolved and removed in the neutralization washing step with alkali. As a result, by pre-wetting powdered polyolefin with a water-soluble acrylic polymer-surfactant mixture and dispersing this in a 1-30% by weight aqueous hydrochloric acid solution, the acrylic polymer can be efficiently applied to the surface of the polyolefin. The surfactant was dissolved in the aqueous hydrochloric acid solution and worked to help disperse the polyolefin particles, making it possible to obtain a hydrochloric acid slurry of polyolefin with good wettability and dispersibility.
塩酸水溶液中の塩酸濃度は1〜30重量%が適当である
が、反応による副生塩酸により濃度が上がるので3〜2
5重量%が好ましい。The appropriate concentration of hydrochloric acid in the hydrochloric acid aqueous solution is 1 to 30% by weight, but since the concentration increases due to the by-product hydrochloric acid from the reaction, the concentration should be 3 to 2% by weight.
5% by weight is preferred.
この際、アクリル系重合体単独では分散能力が足りない
ので界面活性剤として非イオン性、アニオン性活性剤ざ
らにアニオン性スチレン重合体の併用が望ましい。但し
界面活性剤の使用量は系の泡立ちをおさえるためできる
だけ少量にすべきである。At this time, since the acrylic polymer alone does not have sufficient dispersion ability, it is desirable to use an anionic styrene polymer in addition to a nonionic or anionic surfactant as a surfactant. However, the amount of surfactant used should be as small as possible in order to suppress foaming of the system.
本発明による水溶性アクリル系重合体−界面活性剤混合
液は、それぞれ固形分でアクリル系重合体0.3〜2.
0重量%、界面活性剤0.1〜2.0重量%、水99.
6〜96.0重量%の割合が好ましい。The water-soluble acrylic polymer-surfactant mixture according to the present invention has a solid content of 0.3 to 2.0% of the acrylic polymer, respectively.
0% by weight, surfactant 0.1-2.0% by weight, water 99.
A proportion of 6 to 96.0% by weight is preferred.
ポリオレフィンの湿潤処理は、ヘンシェルミキサー、リ
ボンミキサー等の混合機を用いてポリオレフィン100
重量部に対して上記混合液30〜70重量部を十分に混
合して両者をよくなじませる。この際、ポリオレフィン
の湿潤状態はポリオレフィンが完全に湿る状態から餅状
が好ましく、余分な水分がない様にすることが本発明の
重点でおり、水分量が多すぎるとフリーのアクリル系重
合体が存在して望ましくない。Wet processing of polyolefin is performed using a mixer such as a Henschel mixer or a ribbon mixer.
Thoroughly mix 30 to 70 parts by weight of the above-mentioned mixed liquid with respect to the parts by weight to blend the two well. At this time, the wet state of the polyolefin is preferably a state in which the polyolefin is completely wet to a cake-like state, and the emphasis of the present invention is to avoid excess water. If the water content is too high, free acrylic polymer exists and is undesirable.
次にポリオレフィンを撹拌下に塩酸水溶液中に徐々に加
えると細かく分散した濡れ性の良好なポリオレフィンの
塩酸スラリー液を得ることができる。Next, by gradually adding the polyolefin to the aqueous hydrochloric acid solution while stirring, a finely dispersed polyolefin hydrochloric acid slurry with good wettability can be obtained.
塩酸スラリー液中のポリオレフィン濃度は、塩素化反応
時の撹拌を考慮すると3〜20重量%が好ましい。ざら
にこの様にして調整したポリオレフィンの塩酸スラリー
液はポリオレフィンの融点付近の高温(約130℃)に
ざらしても、熱安定性が非常に良く、70ツキングや反
応器壁の付着等の異常は起らない。また撹拌下において
も泡立ちは少なくポリオレフィン粒子は良好なスラリー
状であった。The polyolefin concentration in the hydrochloric acid slurry is preferably 3 to 20% by weight in consideration of stirring during the chlorination reaction. The hydrochloric acid slurry of polyolefin prepared in this way has very good thermal stability even when heated to a high temperature (approximately 130°C) near the melting point of polyolefin, and does not cause abnormalities such as 70° cracking or adhesion to the reactor wall. doesn't happen. Further, even under stirring, there was little foaming and the polyolefin particles were in a good slurry form.
本発明によるポリオレフィンの塩素化方法としては、従
来法のようなポリオレフィン粒子のブロッキングを避け
るために原料ポリオレフィンの融点より10℃以上低い
温度で塩素化反応を行ったり、均一な塩素化を行うため
反応を2段、3段と変化させたり、途中にポリオレフィ
ン融点でのア二〜ル等の作業を行う必要はなく、60〜
150’Cの範囲で塩素化反応を実施できる。例えば1
20〜135°Cの様な高温からでも塩素化反応を始め
ることがてき、反応の進行とともに反応熱による昇温で
150°Cまで可能である。In the method for chlorinating polyolefin according to the present invention, the chlorination reaction is carried out at a temperature 10°C or more lower than the melting point of the raw material polyolefin in order to avoid blocking of polyolefin particles as in conventional methods, and the reaction is carried out at a temperature 10°C or more lower than the melting point of the raw material polyolefin. There is no need to change the temperature in two or three stages, or to perform operations such as annealing at the melting point of the polyolefin during the process.
The chlorination reaction can be carried out in the range of 150'C. For example 1
The chlorination reaction can be started even at a high temperature of 20 to 135°C, and as the reaction progresses, the temperature can be raised up to 150°C due to the heat of reaction.
所定の塩素含有量まで塩素化されたスラリー状の反応生
成物は取り出されン戸別して反応生成物と反応液(塩酸
水溶液)とに分ける。反応生成物は10〜48重量%の
苛性ソーダ水溶液て空温〜100’Cで中和し、次にン
戸別後、空温〜100°Cで水洗し、乾燥して塩素化ポ
リオレフィンの製品とする・また得られた製品のブロッ
キング性を防止するためステアリン酸又はその塩等を添
加することかできる。The slurry-like reaction product, which has been chlorinated to a predetermined chlorine content, is taken out and separated into the reaction product and the reaction solution (hydrochloric acid aqueous solution). The reaction product is neutralized with a 10-48% by weight aqueous solution of caustic soda at air temperature to 100°C, then separated, washed with water at air temperature to 100°C, and dried to produce a chlorinated polyolefin product. -Stearic acid or a salt thereof can also be added to prevent blocking properties of the obtained product.
(発明の効果)
本発明によればポリオレフィン粒子の表面を特定の分散
液で処理することにより、水性懸濁法による塩素化の際
、良好な分散状態が保たれブロッキング現象を起すこと
なく均一な塩素化が可能となる。したがってポリオレフ
ィンを高温塩素化できるため反応速度が早くなり反応時
間が大幅に短縮される。このように高温短時間反応によ
り熱履歴を長時間受けていないため、均一に塩素化され
た原料ポリオレフィンとほぼ同等の細かい粒子か得られ
、そのアルカリによる副生塩酸の中和性。(Effects of the Invention) According to the present invention, by treating the surface of polyolefin particles with a specific dispersion liquid, a good dispersion state is maintained during chlorination using an aqueous suspension method, and a uniform dispersion is achieved without causing a blocking phenomenon. Chlorination becomes possible. Therefore, since polyolefins can be chlorinated at high temperatures, the reaction rate is increased and the reaction time is significantly shortened. Because it is not subjected to a long thermal history due to the high-temperature, short-time reaction, fine particles almost equivalent to the uniformly chlorinated raw material polyolefin can be obtained, and the by-product hydrochloric acid can be neutralized by the alkali.
水による洗浄性が非常に良好となる。ざらにポリオレフ
ィンに定着したアクリル系重合体はアルカリ液に溶解す
るので中和洗浄工程でほぼ完全に除去できる。界面活性
剤も同様である。Washability with water is very good. Since the acrylic polymer fixed on the polyolefin is soluble in the alkaline solution, it can be almost completely removed in the neutralization cleaning step. The same applies to surfactants.
この様にして得られた塩素化ポリオレフィンは従来法に
よるものと比較してブロッキング物や過塩素化物が非常
に少ないこと、均一に塩素化されていること、中和洗浄
が十分に行えることにより熱的安定性に優れているとい
う特徴を有する。The chlorinated polyolefin obtained in this way contains very few blocking substances and perchlorinated substances, is uniformly chlorinated, and can be sufficiently neutralized and washed when heated. It is characterized by excellent physical stability.
本発明による塩素化法は、高温塩素化できることから特
にポリオレフィンの結晶をなくしたゴム質塩素化ポリオ
レフィンの製造に適している。The chlorination method according to the present invention is particularly suitable for producing a rubbery chlorinated polyolefin free of polyolefin crystals since it can be chlorinated at a high temperature.
(実施例) 以下実施例、比較例により本発明を説明する。(Example) The present invention will be explained below with reference to Examples and Comparative Examples.
鋼中組成%及び部はいずれも重量単位である。All composition percentages and parts in steel are by weight.
実施例1〜4
表1に示したポリエチレン、ポリエチレン−7テン共重
合物等のポリオレフィンをリボンミキサー中に入れ、回
転撹拌下に表2の分散液を徐々に加え、表3に示す割合
で混合し均一な湿潤状態のポリオレフィンを得た。Examples 1 to 4 Polyolefins such as polyethylene and polyethylene-7-tene copolymer shown in Table 1 were placed in a ribbon mixer, and the dispersion liquid shown in Table 2 was gradually added with rotational stirring, and mixed in the proportions shown in Table 3. A uniformly wet polyolefin was obtained.
このポリオレフィンを表3の割合で塩酸水溶液中に撹拌
しながら徐々に加え十分に分散せしめた。This polyolefin was gradually added to an aqueous hydrochloric acid solution in the proportions shown in Table 3 with stirring and thoroughly dispersed.
この様にして調整したポリオレフィンの塩酸スラリー液
を100.+7グラスライニング加圧反応容器に入れ、
撹拌下に所定温度まで昇温してからエアーパージし、塩
素ガスを導入して塩素含量30〜40%になるように反
応を行った。The polyolefin hydrochloric acid slurry prepared in this way was mixed with 100. Place in +7 glass lined pressurized reaction vessel,
After raising the temperature to a predetermined temperature with stirring, air purging was performed, and chlorine gas was introduced to conduct a reaction so that the chlorine content was 30 to 40%.
塩素ガスの導入は反応容器上部から(上吹き込み)又は
下部から(下吹き込み)を行った。反応終了後の反応容
器内壁への塩素化ポリオレフィンの付着はほとんど見ら
れなかった。反応時の泡立ちの状態、ブロッキングの状
態、塩素化時間等を表3に示す。Chlorine gas was introduced from the top of the reaction vessel (top blowing) or from the bottom (bottom blowing). Almost no chlorinated polyolefin was observed to adhere to the inner wall of the reaction vessel after the reaction was completed. Table 3 shows the foaming state, blocking state, chlorination time, etc. during the reaction.
次に反応生成物と反応液(仕込み塩酸と副生塩酸との混
合液)とをン戸別し、反応生成物は濃度20%の苛性ソ
ーダ水溶液で50℃撹拌下に全180flで中和洗浄し
、その後80℃の温水で洗浄してから、塩素化ポリオレ
フィン100部にステアリン酸カルシウム1部を添加し
乾燥した。その結果表4に示すような白色微粉末状の塩
素化ポリオレフィンを得た。Next, the reaction product and the reaction solution (a mixed solution of the charged hydrochloric acid and the by-product hydrochloric acid) were separated, and the reaction product was neutralized and washed with a 20% aqueous solution of caustic soda in a total of 180 fl under stirring at 50°C. After washing with warm water at 80° C., 1 part of calcium stearate was added to 100 parts of chlorinated polyolefin and dried. As a result, a white fine powder chlorinated polyolefin as shown in Table 4 was obtained.
比較例1,2
100.11グラスライニング加圧反応容器に表3に示
す割合で水と分散液とを仕込み、撹拌下に表1のポリエ
チレンを徐々に加えた。この時比較例1は泡立ちが多く
、比較例1,2ともポリエチレンの濡れが悪いため上層
部を回っており分散性が悪い。Comparative Examples 1 and 2 A 100.11 glass-lined pressurized reaction vessel was charged with water and a dispersion liquid in the proportions shown in Table 3, and the polyethylene shown in Table 1 was gradually added while stirring. At this time, Comparative Example 1 had a lot of foaming, and both Comparative Examples 1 and 2 had poor wetting of the polyethylene, so they circulated around the upper layer and had poor dispersibility.
次に110°Cまで昇温し、エアーパージ後反応容器上
部から(上部吹き込み)塩素ガスを導入して塩素含量2
0%まで塩素化し、塩素ガスを入れずに130℃まで昇
温し30分間アニールを行った後、120’Cまで冷却
してから再度塩素ガスを導入し塩素含量35%まで反応
を行った。当初の反応温度を′110°Cとしたのはこ
れ以上の温度で塩素化反応を行うとポリエチレンのブロ
ッキング現象を生じ好ましくないからである。Next, the temperature was raised to 110°C, and after air purging, chlorine gas was introduced from the top of the reaction vessel (top blow) to reduce the chlorine content to 2.
After chlorination to 0%, the temperature was raised to 130° C. without introducing chlorine gas, and annealing was performed for 30 minutes. After cooling to 120° C., chlorine gas was introduced again to conduct a reaction until the chlorine content was 35%. The reason why the initial reaction temperature was set at 110 DEG C. is that if the chlorination reaction is carried out at a temperature higher than this, a blocking phenomenon of polyethylene will occur, which is undesirable.
塩素化終了後、反応容器内の気相部分の壁に帯状にポリ
オレフィンのブロッキング物が付着していた。After the chlorination was completed, a band of polyolefin blocking material was found attached to the wall of the gas phase portion of the reaction vessel.
苛性ソーダによる中和は、塩素化ポリエチレン粒子がブ
ロッキングしているためと、反応による長時間の熱履歴
を受けたために表面が硬くなり、中和温度を80℃まで
上げて行った。後工程は実施例と同様である。Neutralization with caustic soda was performed by raising the neutralization temperature to 80° C. because the surface became hard due to the blocking of the chlorinated polyethylene particles and the long-term thermal history caused by the reaction. Post-processes are the same as in the examples.
〈物性試験〉
実施例1〜4.比較例1,2の塩素化ポリオレフィンを
130’Cの2本ロールで5分間練り、分出したシート
を150°C、100k(J/ cutで10分間熱プ
レスして150X 150X 2mm厚の成形シートを
作成した。上記シートについて各物性試験を行った結果
を表4に示す。<Physical property test> Examples 1 to 4. The chlorinated polyolefins of Comparative Examples 1 and 2 were kneaded with two rolls at 130'C for 5 minutes, and the separated sheet was heat-pressed at 150°C and 100K (J/cut) for 10 minutes to form a 150X 150X 2mm thick molded sheet. Table 4 shows the results of various physical property tests performed on the above sheet.
表 1 原料ポリオレフィン
表 2 水溶性アクリル系重合体−界面活性剤混合
液
* アクリル系重合体水溶液
■ アクリル酸重合体水溶液
分子量 13,000 固形分 30%■ アク
リル酸共重合体のアンモニウム塩水溶液分子量 27.
000 固形分 30%界面活性剤
■ 非イオン活性剤:ポリオキシエチレンアルキルフ
ェニルエーテル■ アニオン活性剤:アルキルベンゼ
ンスルホン酸ソーダ塩有効成分 30%
表 3 反応液組成及び塩素化反応
表 4 物 性 試 験
* 硬 度:ショアーA硬度
熱安定性:分出しシートの両面にPETフィルム(30
m)を貼り120℃、 10100kで5分間熱プレ
スしたものを5cmM (厚み2閤)に切り、190℃
ギヤーオーブン中で部分、器、(資)分放置後の外観を
色変化で調べた。Table 1 Raw material polyolefin Table 2 Water-soluble acrylic polymer-surfactant mixture* Acrylic polymer aqueous solution■ Acrylic acid polymer aqueous solution molecular weight 13,000 Solid content 30%■ Acrylic acid copolymer ammonium salt aqueous solution molecular weight 27 ..
000 Solid content 30% Surfactant ■ Nonionic surfactant: Polyoxyethylene alkyl phenyl ether ■ Anionic surfactant: Alkylbenzenesulfonic acid sodium salt Active ingredient 30% Table 3 Reaction liquid composition and chlorination reaction table 4 Physical properties test * Hardness: Shore A hardness Thermal stability: PET film (30
M) was pasted and heat pressed at 120°C and 10100k for 5 minutes, then cut into 5cmM (2 pieces thick) and heated at 190°C.
After being left in a gear oven, the appearance of the parts, vessels, and (materials) was examined by color change.
O変色全くなし
Oわずかに黄変
Δ 黄変
× 褐色変
以上、表3,4により実施例1〜4は比較例1゜2に比
ベポリオレフィンの濡れ性2分散性が良く、比較的高温
でもスラリー液は安定で塩素化反応が進行した。また反
応生成物の粒子が細かいためと、反応時間が短いことに
よる熱履歴が短時間であることにより粒子が比較的ポー
ラス状になっているためかアルカリによる中和は低温で
短時間で終了した。O No discoloration at all O Slight yellowing Δ Yellowing The slurry liquid was stable and the chlorination reaction progressed. In addition, neutralization with alkali was completed in a short time at low temperature, probably because the particles of the reaction product were fine and the particles were relatively porous due to the short thermal history caused by the short reaction time. .
物性においては、実施例2,3と比較例1,2が同一ポ
リエチレンを用いており、はぼ同等の物性を示すが、熱
安定性において本発明による実施例2,3が優れている
ことが判る。In terms of physical properties, Examples 2 and 3 and Comparative Examples 1 and 2 use the same polyethylene and show almost the same physical properties, but Examples 2 and 3 according to the present invention are superior in thermal stability. I understand.
Claims (2)
際し、原料液として粉末状ポリオレフィンを予め水溶性
アクリル系重合体−界面活性剤混合液で湿潤処理し塩酸
水溶液中に分散せしめたスラリー液を使用することを特
徴とする改良された塩素化ポリオレフィンの製造法。(1) When polyolefin is chlorinated by the aqueous suspension method, a slurry liquid in which powdered polyolefin is pre-wetted with a water-soluble acrylic polymer-surfactant mixture and dispersed in an aqueous hydrochloric acid solution is used as the raw material liquid. An improved method for producing a chlorinated polyolefin, characterized by:
α−オレフィンの共重合体又はα−オレフィンとアクリ
ル酸エステルもしくは酢酸ビニールとの共重合体である
請求項1に記載の製造法。(2) the polyolefin is an α-olefin homopolymer,
The production method according to claim 1, which is a copolymer of α-olefin or a copolymer of α-olefin and acrylic ester or vinyl acetate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP34084190A JPH0639492B2 (en) | 1990-11-30 | 1990-11-30 | Improved chlorinated polyolefin manufacturing process. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP34084190A JPH0639492B2 (en) | 1990-11-30 | 1990-11-30 | Improved chlorinated polyolefin manufacturing process. |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04209605A true JPH04209605A (en) | 1992-07-31 |
JPH0639492B2 JPH0639492B2 (en) | 1994-05-25 |
Family
ID=18340800
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP34084190A Expired - Lifetime JPH0639492B2 (en) | 1990-11-30 | 1990-11-30 | Improved chlorinated polyolefin manufacturing process. |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0639492B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6298503B1 (en) * | 1999-12-23 | 2001-10-09 | Ching-Lung Hsu | Bed assembly having a shelter |
-
1990
- 1990-11-30 JP JP34084190A patent/JPH0639492B2/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6298503B1 (en) * | 1999-12-23 | 2001-10-09 | Ching-Lung Hsu | Bed assembly having a shelter |
Also Published As
Publication number | Publication date |
---|---|
JPH0639492B2 (en) | 1994-05-25 |
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