JPH0417203B2 - - Google Patents
Info
- Publication number
- JPH0417203B2 JPH0417203B2 JP59046275A JP4627584A JPH0417203B2 JP H0417203 B2 JPH0417203 B2 JP H0417203B2 JP 59046275 A JP59046275 A JP 59046275A JP 4627584 A JP4627584 A JP 4627584A JP H0417203 B2 JPH0417203 B2 JP H0417203B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- vinyl chloride
- parts
- viscosity
- aqueous solution
- 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 19
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 238000007127 saponification reaction Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 8
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 7
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 238000010558 suspension polymerization method Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 230000005484 gravity Effects 0.000 description 9
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000001879 gelation Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- -1 azo compound Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- QLBNZADBIKYTKU-UHFFFAOYSA-N carbonic acid;3-(2-ethylhexylperoxymethyl)heptane Chemical compound OC(O)=O.CCCCC(CC)COOCC(CC)CCCC QLBNZADBIKYTKU-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
〔産業上の利用分野〕
本発明は、塩化ビニルを水性懸濁重合する際
に、特定の４種の懸濁安定剤を併用することによ
り、優れた粒度分布を有し、嵩比重が高いため押
出法がよく、しかも可塑剤吸収性がよいため成型
品のブツが少ない塩化ビニル樹脂を製造する方法
に関する。
〔従来技術〕
塩化ビニル樹脂の押出性を向上させるためには
高嵩比重品が要求される。高嵩比重品を得るため
の重要な要因は懸濁安定剤にあり、高重合度、高
ケン化度ポリビニルアルコール（以下PVAと言
う）を使用すればよいことが知られている。しか
し、高重合度、高ケン化度PVAだけでは、得ら
れた塩化ビニル樹脂の可塑剤吸収性に劣り、多孔
性に乏しく、ゲル化速度が遅いという欠点があ
る。この欠点をおぎなうため相反する効果を発揮
する低重合度低ケン化度PVAを併用する方法、
さらにこれらにセルロース誘導体としてヒドロキ
シプロピルメチルセルロース（以下HPMCと言
う）又はヒドロキシプロピルセルロース（以下
HPCと言う）を併用する方法が知られている
（特開昭57−76008号公報）。しかしながら、上記
従来技術でも、未だ得られた塩化ビニル樹脂の粒
度分布、嵩比重とゲル化性のバランスなどに於て
満足すべき状態にない現状である。
〔発明の目的〕
本発明者等は上記従来技術を改良すべく特に２
種のセルロース誘導体の併用系につき研究し、得
られる塩化ビニル樹脂の粒度分布を改良し、かつ
ゲル化性と嵩比重の実用的バランス範囲を得るた
めの手段を見出したものである。
〔発明の構成〕
本発明は、塩化ビニル単量体100重量部に対し、
懸濁安定剤として、
(a) ４重量％水溶液の粘度が10〜70cpsでケン化
度95モル％以上のPVA0.03〜1.13重量部、
(b) ４重量％水溶液の粘度が４〜10cpsでケン化
度80モル％以下のPVA0.01〜0.06重量部、
(c) HPMC0.003〜0.012重量部及び
(d) HPC0.001〜0.012重量部
を用いることを特徴とする塩化ビニルの懸濁重合
法である。
本発明の特徴は、上記(c)と(d)の併用にあつて、
(c)即ちHPMCが多過ぎるとゲル化性は改良され
が嵩比重は大きくならず、少な過ぎると変化な
く、また(d)即ち、HPCは多過ぎると嵩比重は向
上するがゲル化性は良くならず少な過ぎると変化
がない。さらに(a)、(b)、(c)及び(d)成分の好ましい
割合は重量単位で(c)＋(d)／(a)＋(b)＋(c)＋(d)＝0.1
〜0.2、(d)／(c)＋(d)＝0.2〜0.5、(a)／(a)＋(b)＝0.2
〜0.4である。
次に本発明で使用される重合触媒は通常の油溶
性触媒、例えばベンゾイルパーオキサイド、ラウ
ロイルパーオキサイド、カプロイルパーオキサイ
ド、ジイソプロピルパーオキシジカーボネート、
ジ（２−エチルヘキシル）−パーオキサイドカー
ボネート、ターシヤリ−ブチルパーオキシピバレ
ート、クミルパーオキシネオデカネート等の有機
過酸化物、２，2′−アゾビスイソブチロニトリ
ル、α−α′−アゾビスジメチルバレロニトリル等
のアゾ化合物あるいはそれらの組合せでその使用
量は通常の量で充分である。又本発明の懸濁重合
においては通常蒸留水又は脱イオン水が使用さ
れ、水と塩化ビニルとの割合は水／塩化ビニル比
＝0.8〜2.0がよい。重合温度は、通常の塩化ビニ
ルの懸濁重合が行なわれる温度すなわち50〜70℃
が採用される。
〔実施例〕
実施例中の部及び％はすべて重量基準である。
実施例 １
内容積15m3の重合反応槽に脱イオン水120部、
ラウロイルパーオキサイド0.023部及び分散剤と
して(a)ケン化度95モル％、４％水溶液の20℃にお
ける粘度が30cpsのPVAと(b)ケン化度73モル％、
４％水溶液の20℃における粘度が7cpsのPVAと
(c)２％水溶液の20℃における粘度が50cpsの
HPMCと(d)２％水溶液の20℃における粘度が
6cpsのHPCを第１表に示す様に合計で0.080部装
入した後、空間部の空気を真空ポンプで排除した
後、塩化ビニルを100部仕込み、57.5℃、8.8Kg／
cm2で重合反応を行なわしめ、反応槽内の圧力が６
Kg／cm2になつた時点で未反応モノマーを回収した
後、このスラリーを脱水し、ケーキを乾燥して塩
化ビニル樹脂を得た。得られた塩化ビニル樹脂の
物性を第１表に示す。この樹脂は、100〜150メツ
シユの粒子を71重量％（100〜200メツシユ90重量
％）含有し、粗粒（60メツシユ篩残）及び微粒
（200メツシユ篩通過）のいずれも含有しない優れ
た粒度分布を有し、更に嵩比重が高く、かつゲル
化速度も良好なものであつた。
実施例２及び３
PVA、HPMC及びHPCは実施例１と同じもの
を使用し、分散剤の使用量を第１表に示すように
した以外は実施例１と同様に行なつた。得られた
塩化ビニル樹脂は、実施例１で得たのとほぼ同等
品質のものであつた。得られた塩化ビニル樹脂の
物性を第１表に示す。
比較例 １〜４
分散剤を第１表に示すようにして以外は実施例
１と同様に行なつた。尚、使用した各分散剤は実
施例１と同じものである。
得られた塩化ビニル樹脂の物性を第１表に示
す。
[Industrial Application Field] The present invention achieves excellent particle size distribution and high bulk specific gravity by using four specific types of suspension stabilizers in combination when performing aqueous suspension polymerization of vinyl chloride. The present invention relates to a method for producing vinyl chloride resin that can be easily extruded and has good plasticizer absorption properties, resulting in fewer lumps in molded products. [Prior Art] In order to improve the extrudability of vinyl chloride resin, a product with a high bulk specific gravity is required. An important factor in obtaining a high bulk specific gravity product is the suspension stabilizer, and it is known that polyvinyl alcohol with a high degree of polymerization and high saponification degree (hereinafter referred to as PVA) can be used. However, using PVA with a high degree of polymerization and a high degree of saponification alone has disadvantages in that the resulting vinyl chloride resin has poor plasticizer absorption, poor porosity, and slow gelation rate. In order to overcome this drawback, there is a method of using PVA with a low polymerization degree and a low saponification degree, which have contradictory effects.
In addition, hydroxypropyl methyl cellulose (hereinafter referred to as HPMC) or hydroxypropyl cellulose (hereinafter referred to as HPMC) is added to these cellulose derivatives.
A method is known in which HPC (called HPC) is used in combination (Japanese Patent Application Laid-open No. 76008/1983). However, even with the above-mentioned conventional techniques, the present situation is that the obtained vinyl chloride resin is still not in a satisfactory state with respect to the particle size distribution, the balance between bulk specific gravity and gelling property, etc. [Object of the Invention] In order to improve the above-mentioned prior art, the present inventors have particularly
Through research on systems in which cellulose derivatives are used in combination, we have found a means to improve the particle size distribution of the resulting vinyl chloride resin and to obtain a practical balance between gelling properties and bulk specific gravity. [Structure of the Invention] The present invention provides that, for 100 parts by weight of vinyl chloride monomer,
As a suspension stabilizer, (a) 0.03 to 1.13 parts by weight of PVA with a viscosity of 10 to 70 cps in a 4 wt% aqueous solution and a saponification degree of 95 mol% or more, (b) 0.03 to 1.13 parts by weight of PVA with a viscosity of 4 to 10 cps in a 4 wt% aqueous solution. Suspended weight of vinyl chloride characterized by using 0.01 to 0.06 parts by weight of PVA with a saponification degree of 80 mol% or less, (c) 0.003 to 0.012 parts by weight of HPMC, and (d) 0.001 to 0.012 parts by weight of HPC. It's legal. The feature of the present invention is that when the above (c) and (d) are used in combination,
(c) That is, if HPMC is too large, the gelatinability will be improved but the bulk specific gravity will not increase; if it is too small, there will be no change; If it doesn't get better and it's too little, there will be no change. Furthermore, the preferred ratio of components (a), (b), (c) and (d) is (c) + (d) / (a) + (b) + (c) + (d) = 0.1 in weight units.
~0.2, (d)/(c)+(d)=0.2~0.5, (a)/(a)+(b)=0.2
~0.4. Next, the polymerization catalyst used in the present invention is a conventional oil-soluble catalyst, such as benzoyl peroxide, lauroyl peroxide, caproyl peroxide, diisopropyl peroxydicarbonate,
Organic peroxides such as di(2-ethylhexyl)-peroxide carbonate, tertiary-butyl peroxypivalate, cumyl peroxyneodecanate, 2,2'-azobisisobutyronitrile, α-α'-azo A normal amount of an azo compound such as bisdimethylvaleronitrile or a combination thereof is sufficient. In the suspension polymerization of the present invention, distilled water or deionized water is usually used, and the ratio of water to vinyl chloride is preferably from 0.8 to 2.0. The polymerization temperature is the temperature at which normal suspension polymerization of vinyl chloride is carried out, that is, 50 to 70°C.
will be adopted. [Examples] All parts and percentages in the examples are based on weight. Example 1 120 parts of deionized water was added to a polymerization reaction tank with an internal volume of 15 m 3 .
0.023 part of lauroyl peroxide and as a dispersant (a) PVA with a saponification degree of 95 mol% and a 4% aqueous solution with a viscosity of 30 cps at 20°C, (b) a saponification degree of 73 mol%,
PVA with a viscosity of 7 cps at 20°C in a 4% aqueous solution
(c) The viscosity of a 2% aqueous solution at 20℃ is 50 cps.
The viscosity of HPMC and (d) 2% aqueous solution at 20℃ is
After charging a total of 0.080 parts of 6cps HPC as shown in Table 1, the air in the space was removed using a vacuum pump, and then 100 parts of vinyl chloride was charged, and the temperature was 57.5℃ and 8.8Kg/
The polymerization reaction was carried out at cm2 , and the pressure inside the reaction tank was 6.
After collecting unreacted monomers when the amount reached Kg/cm 2 , the slurry was dehydrated and the cake was dried to obtain a vinyl chloride resin. Table 1 shows the physical properties of the vinyl chloride resin obtained. This resin has an excellent particle size, containing 71% by weight of particles of 100-150 mesh (90% by weight of 100-200 mesh), and contains neither coarse particles (remaining on a 60-mesh sieve) nor fine particles (passing through a 200-mesh sieve). distribution, high bulk specific gravity, and good gelation rate. Examples 2 and 3 The same procedures as in Example 1 were conducted except that the same PVA, HPMC, and HPC as in Example 1 were used, and the amount of dispersant used was changed as shown in Table 1. The obtained vinyl chloride resin had almost the same quality as that obtained in Example 1. Table 1 shows the physical properties of the vinyl chloride resin obtained. Comparative Examples 1 to 4 The same procedure as in Example 1 was conducted except that the dispersant was changed as shown in Table 1. The dispersants used were the same as in Example 1. Table 1 shows the physical properties of the vinyl chloride resin obtained.
【表】
物性の評価は次によつた。
(1) かさ比重：JIS K6721
(2) ゲル化速度：（残存粒子数）
第２表に示す配合物をよく混合し、直径８イン
チ、回転数18／18rpmの２本のロールを145℃に
加熱して0.5ｍ／ｍのロール間隙で混練し、時間
毎に10cm×10cmのシート上に残存する未ゲル化粒
子数の数を数え、短時間でシート上に残存する未
ゲル化粒子の数が少なくなるものをゲル化速度が
速いものとして評価する。
(3) 粒度分布：JIS Ｚ 8801 [Table] Evaluation of physical properties was as follows. (1) Bulk specific gravity: JIS K6721 (2) Gelation rate: (number of remaining particles) The formulations shown in Table 2 were mixed well, and two rolls with a diameter of 8 inches and a rotation speed of 18/18 rpm were heated to 145°C. Heat and knead with a roll gap of 0.5 m/m, count the number of ungelled particles remaining on a 10 cm x 10 cm sheet every time, and calculate the number of ungelled particles remaining on the sheet in a short time. The one in which the gelation rate decreases is evaluated as having a fast gelation rate. (3) Particle size distribution: JIS Z 8801
【表】【table】
本発明の方法により得られる塩化ビニル樹脂
は、ゲル化が早くて微粉特有の問題がなく望まし
い100〜150メツシユの粒子を70重量％以上含有
し、かつ粗粒及び微粒をほとんど含有していない
ので収率が高く、微粉特有のフイルター目詰ま
り、粉立ちなどの問題のない優れた粒度分布を有
していると共に、高い嵩比重と速いゲル化速度を
バランスよく有しているので、高速度での押出が
でき、その場合においても未ゲル化粒子の少ない
成形体を得られるという優れた効果を奏する。
The vinyl chloride resin obtained by the method of the present invention gels quickly and does not have the problems peculiar to fine particles, and contains 70% by weight or more of desirable particles of 100 to 150 mesh, and contains almost no coarse particles or fine particles. It has a high yield and an excellent particle size distribution without problems such as filter clogging and dusting that are typical of fine powders. It also has a good balance of high bulk specific gravity and fast gelling speed, so it can be used at high speeds. can be extruded, and even in this case, it has the excellent effect of obtaining a molded product with a small amount of ungelled particles.
Claims (1)
定剤として、 (a) ４重量％水溶液の粘度が10〜70cpsでケン化
度95モル％以上のポリビニルアルコール0.03〜
1.13重量部、 (b) ４重量％水溶液の粘度が４〜10cpsでケン化
度80モル％以下のポリビニルアルコール0.01〜
0.06重量部、 (c) ヒドロキシプロピルメチルセルロース0.003
〜0.012重量部及び (d) ヒドロキシプロピルセルロース0.001〜0.012
重量部 を用いることを特徴とする塩化ビニルの懸濁重合
法。[Scope of Claims] 1. Based on 100 parts by weight of vinyl chloride monomer, as a suspension stabilizer, (a) polyvinyl alcohol having a viscosity of 4% by weight aqueous solution of 10 to 70 cps and a degree of saponification of 95 mol% or more from 0.03 to
1.13 parts by weight, (b) 0.01 to 0.01% polyvinyl alcohol with a viscosity of 4% by weight aqueous solution of 4 to 10 cps and a degree of saponification of 80 mol% or less
0.06 parts by weight, (c) Hydroxypropyl methylcellulose 0.003
~0.012 part by weight and (d) 0.001~0.012 hydroxypropyl cellulose
A suspension polymerization method for vinyl chloride, characterized in that parts by weight are used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4627584A JPS60190404A (en) | 1984-03-10 | 1984-03-10 | Suspension polymerization of vinyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4627584A JPS60190404A (en) | 1984-03-10 | 1984-03-10 | Suspension polymerization of vinyl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60190404A JPS60190404A (en) | 1985-09-27 |
| JPH0417203B2 true JPH0417203B2 (en) | 1992-03-25 |
Family
ID=12742670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4627584A Granted JPS60190404A (en) | 1984-03-10 | 1984-03-10 | Suspension polymerization of vinyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60190404A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS525886A (en) * | 1975-06-28 | 1977-01-17 | Huels Chemische Werke Ag | Preparation of polyvinyl chloride |
| JPS5510603A (en) * | 1978-07-04 | 1980-01-25 | Ncr Co | Automatic winding spool |
| JPS5550043A (en) * | 1978-10-06 | 1980-04-11 | Adeka Argus Chem Co Ltd | Halogen-containing resin composition |
| JPS5661402A (en) * | 1979-10-23 | 1981-05-26 | Denki Kagaku Kogyo Kk | Suspension stabilizer |
| JPS5672003A (en) * | 1979-11-15 | 1981-06-16 | Mitsui Toatsu Chem Inc | Production of vinyl chloride polymer |
| JPS5761041A (en) * | 1980-09-30 | 1982-04-13 | Mitsubishi Petrochem Co Ltd | Semiconducting resin composition |
| JPS5776008A (en) * | 1980-10-30 | 1982-05-12 | Mitsui Toatsu Chem Inc | Preparation of polyvinyl chloride having high bulk specific gravity |
| JPS591517A (en) * | 1982-06-07 | 1984-01-06 | エア・プロダクツ・アンド・ケミカルズ・インコ−ポレイテツド | Manufacture of vinyl chloride-propylene copolymer |
-
1984
- 1984-03-10 JP JP4627584A patent/JPS60190404A/en active Granted
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS525886A (en) * | 1975-06-28 | 1977-01-17 | Huels Chemische Werke Ag | Preparation of polyvinyl chloride |
| JPS5510603A (en) * | 1978-07-04 | 1980-01-25 | Ncr Co | Automatic winding spool |
| JPS5550043A (en) * | 1978-10-06 | 1980-04-11 | Adeka Argus Chem Co Ltd | Halogen-containing resin composition |
| JPS5661402A (en) * | 1979-10-23 | 1981-05-26 | Denki Kagaku Kogyo Kk | Suspension stabilizer |
| JPS5672003A (en) * | 1979-11-15 | 1981-06-16 | Mitsui Toatsu Chem Inc | Production of vinyl chloride polymer |
| JPS5761041A (en) * | 1980-09-30 | 1982-04-13 | Mitsubishi Petrochem Co Ltd | Semiconducting resin composition |
| JPS5776008A (en) * | 1980-10-30 | 1982-05-12 | Mitsui Toatsu Chem Inc | Preparation of polyvinyl chloride having high bulk specific gravity |
| JPS591517A (en) * | 1982-06-07 | 1984-01-06 | エア・プロダクツ・アンド・ケミカルズ・インコ−ポレイテツド | Manufacture of vinyl chloride-propylene copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60190404A (en) | 1985-09-27 |
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