JPS6336604B2 - - Google Patents
Info
- Publication number
- JPS6336604B2 JPS6336604B2 JP59146166A JP14616684A JPS6336604B2 JP S6336604 B2 JPS6336604 B2 JP S6336604B2 JP 59146166 A JP59146166 A JP 59146166A JP 14616684 A JP14616684 A JP 14616684A JP S6336604 B2 JPS6336604 B2 JP S6336604B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene polymer
- chlorinated
- producing
- ethylene
- elastomer according
- 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
Links
- 229920000573 polyethylene Polymers 0.000 claims description 33
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 19
- 229920001971 elastomer Polymers 0.000 claims description 12
- 239000000806 elastomer Substances 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 9
- 239000012320 chlorinating reagent Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000856 hastalloy Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000010224 classification analysis Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003398 denaturant Substances 0.000 description 1
- -1 di-α-cumel peroxide Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明はエチレン重合体の変性に関する。
〔発明の背景〕
エラストマー塩素化エチレン重合体は、一旦交
差結合すると、(a)溶剤抵抗性、(b)オゾン抵抗性、
(c)耐摩耗性、(d)耐候性、(e)約−20℃から約120℃
に及ぶ広い温度範囲での可撓性などの数多くの望
ましい特性によつて特徴づけられるため、工業的
に魅力のある物質である。従つて、硬化された塩
素化エチレン重合体及びそれを基にした組成物
は、上記のすぐれた特性のために多くの用途、例
えばフイルム材料、線やケーブルなどの押出成形
材、耐炎組成物の基材重合体、ポリ塩化ビニル重
合体などの可塑剤等々に広く用いられている。
従来、塩素化エチレン重合体の製造は、重合体
を溶剤中で塩素化剤と反応させる溶液法によつて
行われている。いわゆる溶液法は、反応終了時に
一般には反応系を溶剤の追出しに十分な高温度で
熱することによつて、溶剤を塩素化重合体から除
去することを必要とする。しかし、溶剤除去温度
では塩素化エチレン重合体は凝集する傾向があ
り、取扱いや処理が困難となる。
〔発明の目的〕
従つて、本発明の目的は、溶剤や希釈剤の使用
を避けることによつてそれらの使用に伴う問題点
を解決し、特性バランスの良い均一塩素化された
粒状のエラストマーエチレン重合体を提供するこ
とにある。本発明の塩素化エチレン重合体は粒状
であることから取扱い及び処理が容易となる。
〔発明の説明〕
本発明の塩素化エチレン重合体は、溶剤や希釈
剤の不存在下に、気体状塩素化剤を、密度約0.87
〜0.92ｇ／c.c.、好ましくは0.89〜0.91ｇ／c.c.と空
孔容積約0.1〜１c.c.／ｇ、一般には0.1〜0.5c.c.／
ｇ、より好ましくは0.2〜0.4c.c.／ｇとを有する粒
状のエチレン重合体と反応させることにより、約
2000psi（141Kg／cm2）よりも小さい引張りモジユ
ラスと、約10％より少ない結晶化度とを有する粒
状エラストマー塩素化エチレン重合体を製造す
る。
このようにして製造された塩素化エチレン重合
体は均一に塩素化されていてしかも弾性（エラス
トメリツク）を有するものであり、水性分散体の
形で製造された市販の塩素化エチレン重合体に比
肩しうるすぐれた特性バランスを有する。
上記の密度及び空孔容積を有する本発明の目的
に適するエチレン重合体は、エチレンを少くとも
１つのアルフアモノオレフインと低圧下に反応さ
せることにより得たエチレン―C3〜C8アルフア
オレフイン重合体である。かかる製造法は米国特
許第4302565号、米国特許願第480296号等に記載
されている。
本発明の目的に特に望ましいエチレン重合体は
上記の密度及び空孔容積を有し、さらに約50〜99
モル％、好ましくは約75〜96モル％のエチレン
と、約１〜50モル％、好ましくは約４〜25モル％
のC3〜C8アルフアモノオレフイン（例えばプロ
ピレン、ブテン―１、ペンテン―１、４メチルペ
ンテン―１、ヘキセン―１、ヘプテン―１、及び
オクテン―１）を含有する。
本発明によつて塩素化すべきより望ましいエチ
レン重合体は、
約200〜1500μｍ、好ましくは約300〜1000μｍ
の平均粒子径と、
約10〜30、好ましくは約15〜24lb／ft3（0.16〜
0.48、好ましくは0.24〜0.384ｇ／c.c.）のかさ密度
と、
約0.1〜１c.c.／ｇ、好ましくは約0.1〜0.5c.c.／
ｇ、さらに好ましくは約0.2〜0.4c.c.／ｇの空孔容
積と、
約0.87〜0.92ｇ／c.c.、好ましくは約0.89〜0.91
ｇ／c.c.の密度と、を有する。
気体状塩素化剤による処理時間は、約2000psi
（141Kg／cm2）よりも小さい引張りモジユラスと、
10％より小さい（好ましくは０〜５％）結晶化度
と、約５〜55wt％、好ましくは15〜40wt％の全
塩素含有量とを有する塩素化エチレン重合体を得
るのに十分なものとする。
この処理はエチレン重合体の主鎖の水素原子を
塩素で置換するものと思われる。
処理の実際の時間は塩素化されるエチレン重合
体、使用する塩素化剤、温度及び圧力に依存する
が、約３〜10時間の範囲で変化する。
一般に、適当な温度は約50〜130℃、好ましく
は約50〜100℃である。反応を行う圧力は大気圧
から約70Kg／cm2である。ただしこの場合反応体ま
たは副生物が反応条件下に凝縮しないものとす
る。一般に、温度及び圧力が高い程反応時間は短
い。
反応を行うのに用いる塩素化剤の量は約10〜
200wt％、好ましくは約20〜100wt％（被処理エ
チレン重合体基準）である。
所望により、窒素のような不活性ガスを変性用
気体状塩素ガスと共に用いることにより流動化
剤、分散助剤、除熱材（heatsink）として作用さ
せることができる。
ここで言及する特性は次の方法により測定し
た。
密度（ｇ／c.c.）― ASTM―Ｄ―1505による。
板を作り、100℃で１時間ならして結晶平衡
化に近づけ、密度勾配カラム中で密度の測定
を行つた。
空孔容積（c.c.／ｇ）― ASTM―Ｃ―699―108
（45）による。
平均粒子径（μｍ）― ASTM―Ｄ―1921方法
Ａにより測定した500ｇのサンプルの分級分
析から得たデータから算出。計算はふるい上
に残つた重量分率によつて行つた。
かさ密度（1b／ft3）― 直径9.5mmの漏斗から100
mlの目盛付きシリンダーへ振動しないように
して100ml目盛まで重合体を入れた。かさ密
度はシリンダーの重量と、充填したシリンダ
ーの重量との差から求めた。
結晶化度（％）― デユポン社製990分析器に圧
力微分走査カロリメータ（DSC）セルを付
けたもので測定した。
引張りモジユラス（psi，Kg／cm2）― 4in×4in
×0.020in（10cm×10cm×0.5mm）のフイルムを
130〜150℃で加圧成形し、その１％セカント
（正割）モジユラスをASTM―Ｄ―638によ
り測定した。
引張り強さ（psi，Kg／cm2）― 同様なフイルム
をASTM―Ｄ―638により測定した。
破壊伸び率（％）― 同様なフイルムをASTM
―Ｄ―638により測定した。
〔実施例〕
以下に本発明の実施例を詳しく説明する。
特にことわらない限り、以下の例で用いられる
出発原料であるエチレン重合体は米国特願第
480296号（特公昭62−44004号）に記載された方
法により製造されたものを用いる。
エチレン重合体は、２のガラス内張りステン
レススチールまたはハステロイ合金（55％Ni、
17％Mo、16％Cr、６％Fe及び４％Ｎ）製反応器
に熱電対及び電動式Ｕ形ハステロイ合金撹拌子を
具備したものを用いて塩素化した。
ハステロイ製垂下管（直径２cm）を用いて気体
状変性化剤を反応器に供給した。未反応の変性化
剤及びHClを25％水性NaOHを収容した捕集トラ
ツプへ通気した。気体状変性化剤は約15〜450psi
（1.0〜32Kg／cm2）の圧力下にCl2が８〜15ｇ／hr
の流量となるように供給した。処理すべき重合体
約200〜1000ｇを反応器に装入し、外部ヒーター
により加熱した。これらの例では触媒は用いなか
つた。
重合体を反応器に装入して所望の反応温度に加
熱した後、重合体を撹拌子によりかき混ぜ、気体
状変性化剤を供給した。変性化処理中に、反応器
からサンプルを抽出し、塩素含有量及び結晶化度
を測定した。反応の終了時に、気体状変性化剤の
流れを止め、反応容器を窒素ガスにより掃気して
未反応Cl2及びHCl副生物を除去しながら生成物
を放冷した。
３種の粒状低密度エチレン―ブテン―１共重合
体であつて、次の表に挙げた特性を有するものを
塩素ガスにより塩素化した（サンプルＡ，Ｂ、対
照１）。
This invention relates to the modification of ethylene polymers. BACKGROUND OF THE INVENTION Elastomeric chlorinated ethylene polymers, once cross-linked, exhibit (a) solvent resistance, (b) ozone resistance,
(c) Abrasion resistance, (d) Weather resistance, (e) Approx. -20℃ to approx. 120℃
It is an industrially attractive material because it is characterized by a number of desirable properties, including flexibility over a wide temperature range. Therefore, cured chlorinated ethylene polymers and compositions based thereon have many applications, such as film materials, extruded materials such as wires and cables, and flame-resistant compositions due to the above-mentioned excellent properties. It is widely used as a plasticizer for base polymers, polyvinyl chloride polymers, etc. Conventionally, chlorinated ethylene polymers have been produced by a solution method in which the polymer is reacted with a chlorinating agent in a solvent. The so-called solution process requires that the solvent be removed from the chlorinated polymer at the end of the reaction, generally by heating the reaction system to a temperature sufficiently high to drive off the solvent. However, at solvent removal temperatures, chlorinated ethylene polymers tend to aggregate, making handling and processing difficult. [Object of the Invention] Therefore, the object of the present invention is to solve the problems associated with the use of solvents and diluents by avoiding the use of them, and to produce a uniformly chlorinated granular elastomer ethylene with well-balanced properties. The purpose of this invention is to provide a polymer. Since the chlorinated ethylene polymer of the present invention is granular, it is easy to handle and process. [Description of the Invention] The chlorinated ethylene polymer of the present invention is capable of absorbing a gaseous chlorinating agent in the absence of a solvent or diluent at a density of about 0.87.
~0.92 g/cc, preferably 0.89-0.91 g/cc and a pore volume of about 0.1-1 c.c./g, typically 0.1-0.5 cc/g.
g, more preferably 0.2 to 0.4 cc/g.
A particulate elastomeric chlorinated ethylene polymer is produced having a tensile modulus of less than 2000 psi (141 Kg/cm 2 ) and a crystallinity of less than about 10%. The chlorinated ethylene polymer produced in this way is uniformly chlorinated and has elasticity (elastomerism), which is comparable to commercially available chlorinated ethylene polymers produced in the form of aqueous dispersions. It has an excellent balance of properties. Ethylene polymers suitable for the purposes of the present invention having the above density and pore volume are ethylene- C3 to C8 alpha-olefin polymers obtained by reacting ethylene with at least one alpha-olefin under low pressure. It is. Such manufacturing methods are described in US Patent No. 4,302,565, US Patent Application No. 480,296, etc. Particularly desirable ethylene polymers for purposes of the present invention have densities and pore volumes as described above, and further have a density and a pore volume of about 50 to 99
mol%, preferably about 75-96 mol% ethylene and about 1-50 mol%, preferably about 4-25 mol%
of C3 to C8 alpha monoolefins (e.g., propylene, 1-butene, 1-pentene, 4-methylpentene-1, hexene-1, heptene-1, and octene-1). More desirable ethylene polymers to be chlorinated according to the present invention have a diameter of about 200 to 1500 μm, preferably about 300 to 1000 μm.
with an average particle size of about 10 to 30, preferably about 15 to 24 lb/ ft3 (0.16 to
0.48, preferably 0.24 to 0.384 g/cc) and about 0.1 to 1 c.c./g, preferably about 0.1 to 0.5 cc/g.
g, more preferably about 0.2-0.4 cc/g, and about 0.87-0.92 g/cc, preferably about 0.89-0.91
It has a density of g/cc. Treatment time with gaseous chlorinating agent is approximately 2000 psi
(141Kg/cm 2 ),
Sufficient to obtain a chlorinated ethylene polymer having a crystallinity of less than 10% (preferably 0-5%) and a total chlorine content of about 5-55 wt%, preferably 15-40 wt%. do. This treatment appears to replace hydrogen atoms in the main chain of the ethylene polymer with chlorine. The actual time of treatment depends on the ethylene polymer being chlorinated, the chlorinating agent used, the temperature and pressure, and will vary from about 3 to 10 hours. Generally, suitable temperatures are about 50-130°C, preferably about 50-100°C. The pressure at which the reaction is carried out is from atmospheric pressure to about 70 Kg/cm 2 . In this case, however, no reactants or by-products condense under the reaction conditions. Generally, the higher the temperature and pressure, the shorter the reaction time. The amount of chlorinating agent used to carry out the reaction is approximately 10 to
200 wt%, preferably about 20 to 100 wt% (based on the ethylene polymer to be treated). If desired, an inert gas such as nitrogen can be used with the modifying gaseous chlorine gas to act as a fluidizing agent, dispersing aid, and heatsink. The properties mentioned here were measured by the following method. Density (g/cc) - According to ASTM-D-1505.
A plate was prepared and conditioned at 100°C for 1 hour to approach crystal equilibrium, and the density was measured in a density gradient column. Pore volume (cc/g) - ASTM-C-699-108
According to (45). Average particle size (μm) - Calculated from data obtained from classification analysis of a 500 g sample measured according to ASTM-D-1921 Method A. Calculations were made by the weight fraction remaining on the sieve. Bulk density (1b/ ft3 ) - 100 from a 9.5mm diameter funnel
The polymer was poured into a cylinder with ml graduations up to the 100 ml graduation without vibration. The bulk density was determined from the difference between the weight of the cylinder and the weight of the filled cylinder. Crystallinity (%) - Measured using a DuPont 990 analyzer equipped with a pressure differential scanning calorimeter (DSC) cell. Tensile modulus (psi, Kg/ cm2 ) - 4in x 4in
x0.020in (10cm x 10cm x 0.5mm) film
It was pressure-molded at 130 to 150°C, and its 1% secant modulus was measured according to ASTM-D-638. Tensile Strength (psi, Kg/cm 2 ) - Similar films were measured according to ASTM-D-638. Fracture elongation (%) - ASTM similar film
- Measured using D-638. [Example] Examples of the present invention will be described in detail below. Unless otherwise specified, the starting material ethylene polymer used in the following examples is
The one manufactured by the method described in No. 480296 (Japanese Patent Publication No. 62-44004) is used. The ethylene polymer is made of glass-lined stainless steel or Hastelloy alloy (55% Ni,
Chlorination was carried out using a reactor made of 17% Mo, 16% Cr, 6% Fe and 4% N, equipped with a thermocouple and an electric U-shaped Hastelloy alloy stirrer. The gaseous modifying agent was fed into the reactor using a Hastelloy down tube (2 cm diameter). Unreacted denaturant and HCl were vented into a collection trap containing 25% aqueous NaOH. Gaseous modifiers are approximately 15 to 450 psi
8-15g/hr of Cl2 under pressure of (1.0-32Kg/ cm2 )
The flow rate was as follows. Approximately 200-1000 g of the polymer to be treated was charged to the reactor and heated by an external heater. No catalyst was used in these examples. After the polymer was charged into the reactor and heated to the desired reaction temperature, the polymer was stirred with a stirrer and the gaseous modifier was fed. During the modification process, samples were extracted from the reactor and the chlorine content and crystallinity were determined. At the end of the reaction, the flow of gaseous modifier was stopped and the product was allowed to cool while the reaction vessel was purged with nitrogen gas to remove unreacted Cl 2 and HCl byproducts. Three particulate low density ethylene-butene-1 copolymers having the properties listed in the following table were chlorinated with chlorine gas (Samples A, B, Control 1).
【表】
エチレン―ブテン―１共重合体はCl2ガスと約
８〜14時間、70〜80℃の温度で反応させて塩素化
した（対照１及びサンプルＡの場合）。またサン
プルＢの場合には上記温度を60℃とした。表の
結果を得た。サンプルＡ，Ｂに対応して実施例
１，２とする。Table Ethylene-butene-1 copolymer was chlorinated by reacting with Cl 2 gas for about 8-14 hours at a temperature of 70-80°C (for Control 1 and Sample A). In the case of sample B, the above temperature was 60°C. Obtained the results in the table. Examples 1 and 2 correspond to samples A and B.
【表】
いる塩素化ポリエチレン
対照１の塩素化重合体は高い引張りモジユラス
から分るように弾性体（エラストマー）ではな
い。これに対し、本発明に従つて製造されたエラ
ストマーは市販の塩素化重合体と比肩しうる特性
を有することが分る。
規定の空孔容積及び密度を有するエチレン重合
体を用いる必要性をさらに例示するために、対照
３の実験を、次の特性を有する粒状エチレンを用
いて行つた。
密度（ｇ／c.c.） 0.968
結晶化度（％） 0.3
平均粒子径（μｍ） 0.3
空孔率（c.c.／ｇ） 0.3
かさ密度 1b／ft3 27
（ｇ／c.c.） （0.432）
この重合体を85〜90℃で塩素ガスにより塩素化
して下記の特性を有する塩素化重合体を得た。Table: Chlorinated Polyethylene The chlorinated polymer of Control 1 is not an elastomer, as evidenced by its high tensile modulus. In contrast, elastomers made in accordance with the present invention are found to have properties comparable to commercially available chlorinated polymers. To further illustrate the need to use ethylene polymers with defined pore volumes and densities, a control 3 experiment was conducted using granular ethylene with the following properties. Density (g/cc) 0.968 Crystallinity (%) 0.3 Average particle size (μm) 0.3 Porosity (cc/g) 0.3 Bulk density 1b/ft 3 27 (g/cc) (0.432) This polymer is 85 Chlorination was carried out with chlorine gas at ~90°C to obtain a chlorinated polymer having the following properties.
【表】【table】
【表】
引張り強さ
（psi） 3470 1900 3270
（Kg／cm2） (244) (133) (230)
伸び率 （％） 420 13 2
.7
対照３を示す表の結果から、塩素化重合体が
比較的高い塩素化含有率を有するからと言つて、
エラストマーになるとは言えないことが分る。
同様な実験を、次に示す特性を有する粒状エチ
レン―ブテン―１共重合体より成る対照４に対し
て行つた。
密度（ｇ／c.c.） 0.935
共重合体中のブテン―１（モル％） 1.5
結晶化度（％） 56.5
平均粒子径（μｍ） 500
空孔率（c.c.／ｇ） 0.35
かさ密度（1b／ft3） 26
（ｇ／c.c.） （0.416）
この共重合体を塩素ガスを用いて90℃にて塩素
化して表の特性を有する塩素化重合体を得た。[Table] Tensile strength (psi) 3470 1900 3270
(Kg/ cm2 ) (244) (133) (230)
Growth rate (%) 420 13 2
.7
The results in the table showing Control 3 show that even though the chlorinated polymer has a relatively high chlorination content,
It turns out that it cannot be said that it will become an elastomer. A similar experiment was conducted on Control 4, which consisted of a particulate ethylene-butene-1 copolymer having the following properties: Density (g/cc) 0.935 Butene-1 in copolymer (mol%) 1.5 Crystallinity (%) 56.5 Average particle size (μm) 500 Porosity (cc/g) 0.35 Bulk density (1b/ft 3 ) 26 (g/cc) (0.416) This copolymer was chlorinated using chlorine gas at 90°C to obtain a chlorinated polymer having the properties shown in the table.
【表】
対照４の結果を示す表から、塩素化重合体の
塩素含有率が比較的高いからと言つて、エラスト
マーではないことが分る。なお、対照１，３，４
及びサンプルＡは米国特許第4302565号の方法に
従つて製造した。
本発明の塩素化エチレン重合体は当分野で周知
のジ―α―クメルパーオキサイド等の過酸化物を
用いて交差結合させることができる。
以上のように、本発明によると、ガス状塩素化
剤を用いて溶液内反応によるものと同様なすぐれ
たエラストマー塩素化エチレン重合体または共重
合体を提供することができ、且つプロセス上のメ
リツトも多いものである。[Table] From the table showing the results of Control 4, it can be seen that even though the chlorinated polymer has a relatively high chlorine content, it is not an elastomer. In addition, controls 1, 3, 4
and Sample A were prepared according to the method of US Pat. No. 4,302,565. The chlorinated ethylene polymers of the present invention can be cross-linked using peroxides such as di-α-cumel peroxide, which are well known in the art. As described above, according to the present invention, it is possible to provide an excellent elastomeric chlorinated ethylene polymer or copolymer similar to that obtained by in-solution reaction using a gaseous chlorinating agent, and there are advantages in the process. There are also many.
Claims (1)
空孔容積とを有する粒状エチレン重合体を、ガス
状塩素化剤と反応させることを特徴とする、
2000psi（141Kg／cm2）よりも小さい引張りモジユ
ラスと10％よりも小さい結晶化度とを有する粒状
の塩素化エチレン重合体エラストマーの製造法。 ２ 粒状エチレン重合体は、0.1〜0.5c.c.／ｇの空
孔容積を有するエチレン−C3ないしC8アルフア
オレフイン重合体である前記第１項記載の塩素化
エチレン重合体エラストマーの製造法。 ３ 密度は0.89〜0.91ｇ／c.c.であり、空孔容積は
0.2〜0.4c.c.／ｇである前記第２項記載の塩素化エ
チレン重合体エラストマーの製造法。 ４ 塩素化剤は塩素ガスである前記第１項または
第２項記載の塩素化エチレン重合体エラストマー
の製造法。 ５ エチレン重合体はエチレン―ブテン―１共重
合体である前記第１または２項記載の塩素化エチ
レン重合体エラストマーの製造法。 ６ 塩素化は50〜130℃の温度で行われる前記第
１項ないし第５項のいずれかに記載の塩素化エチ
レン重合体エラストマーの製造法。 ７ エチレン重合体は200〜1500μｍの平均粒子
径と、10〜30のかさ密度とを有する前記第１項ま
たは第２項記載の塩素化エチレン重合体エラスト
マーの製造法。[Claims] 1. A particulate ethylene polymer having a density of 0.87 to 0.92 g/cc and a pore volume of 0.1 to 1.0 cc/g is reacted with a gaseous chlorinating agent,
A method for producing particulate chlorinated ethylene polymer elastomers having a tensile modulus of less than 2000 psi (141 Kg/cm 2 ) and a crystallinity of less than 10%. 2. The method for producing a chlorinated ethylene polymer elastomer according to item 1 above, wherein the granular ethylene polymer is an ethylene- C3 to C8 alpha olefin polymer having a pore volume of 0.1 to 0.5 cc/g. 3 The density is 0.89-0.91g/cc, and the pore volume is
2. The method for producing a chlorinated ethylene polymer elastomer according to item 2 above, wherein the amount is 0.2 to 0.4 cc/g. 4. The method for producing a chlorinated ethylene polymer elastomer according to item 1 or 2 above, wherein the chlorinating agent is chlorine gas. 5. The method for producing a chlorinated ethylene polymer elastomer according to item 1 or 2 above, wherein the ethylene polymer is an ethylene-butene-1 copolymer. 6. The method for producing a chlorinated ethylene polymer elastomer according to any one of items 1 to 5 above, wherein the chlorination is carried out at a temperature of 50 to 130°C. 7. The method for producing a chlorinated ethylene polymer elastomer according to item 1 or 2 above, wherein the ethylene polymer has an average particle diameter of 200 to 1500 μm and a bulk density of 10 to 30.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US51433783A | 1983-07-15 | 1983-07-15 | |
| US514337 | 1983-07-15 | ||
| US608875 | 1984-05-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6076505A JPS6076505A (en) | 1985-05-01 |
| JPS6336604B2 true JPS6336604B2 (en) | 1988-07-21 |
Family
ID=24046748
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14616584A Granted JPS6076509A (en) | 1983-07-15 | 1984-07-16 | Manufacture of elastomer chlorosulfonated ethylene polymer |
| JP14616684A Granted JPS6076505A (en) | 1983-07-15 | 1984-07-16 | Manufacture of chlorinated ethylene polymer elastomer |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14616584A Granted JPS6076509A (en) | 1983-07-15 | 1984-07-16 | Manufacture of elastomer chlorosulfonated ethylene polymer |
Country Status (2)
| Country | Link |
|---|---|
| JP (2) | JPS6076509A (en) |
| ZA (2) | ZA845448B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61120810A (en) * | 1984-11-16 | 1986-06-07 | Denki Kagaku Kogyo Kk | Production of chlorosulfonated polyolefin |
| JP4170106B2 (en) * | 2003-02-04 | 2008-10-22 | 花王株式会社 | Porous particles and cosmetics |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4847589A (en) * | 1971-10-14 | 1973-07-06 | ||
| JPS4947038A (en) * | 1972-09-12 | 1974-05-07 | ||
| JPS5228476A (en) * | 1975-08-29 | 1977-03-03 | Fujitsu Ltd | Liquid phase growth apparatus |
| JPS5556110A (en) * | 1978-10-20 | 1980-04-24 | Nippon Oil Co Ltd | Preparation of copolymer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0133686A1 (en) * | 1983-08-04 | 1985-03-06 | The B.F. GOODRICH Company | Chlorosulfonated polyolefin process |
-
1984
- 1984-07-13 ZA ZA845448A patent/ZA845448B/en unknown
- 1984-07-13 ZA ZA845447A patent/ZA845447B/en unknown
- 1984-07-16 JP JP14616584A patent/JPS6076509A/en active Granted
- 1984-07-16 JP JP14616684A patent/JPS6076505A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4847589A (en) * | 1971-10-14 | 1973-07-06 | ||
| JPS4947038A (en) * | 1972-09-12 | 1974-05-07 | ||
| JPS5228476A (en) * | 1975-08-29 | 1977-03-03 | Fujitsu Ltd | Liquid phase growth apparatus |
| JPS5556110A (en) * | 1978-10-20 | 1980-04-24 | Nippon Oil Co Ltd | Preparation of copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA845447B (en) | 1985-03-27 |
| JPS6076505A (en) | 1985-05-01 |
| ZA845448B (en) | 1985-03-27 |
| JPS6343405B2 (en) | 1988-08-30 |
| JPS6076509A (en) | 1985-05-01 |
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