JPH035422B2 - - Google Patents
Info
- Publication number
- JPH035422B2 JPH035422B2 JP11294883A JP11294883A JPH035422B2 JP H035422 B2 JPH035422 B2 JP H035422B2 JP 11294883 A JP11294883 A JP 11294883A JP 11294883 A JP11294883 A JP 11294883A JP H035422 B2 JPH035422 B2 JP H035422B2
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- pvc
- polymerization
- vinyl chloride
- weight
- 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
- 229920001577 copolymer Polymers 0.000 claims description 17
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 11
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- DDMBAIHCDCYZAG-UHFFFAOYSA-N butyl 7,7-dimethyloctaneperoxoate Chemical group CCCCOOC(=O)CCCCCC(C)(C)C DDMBAIHCDCYZAG-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- -1 ethylene, propylene, vinyl Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、塩化ビニル系樹脂（以下PVCと略
記する）の体積抵抗率（以下VRと略記する）を
向上させた組成物に関する。
元来、PVCは体積抵抗率の大きいプラスチツ
クであり、電気絶縁材料として使用されている
が、PVCの製造工程や加工工程での微量の金属
イオンや比較イオン化傾向の高い金属化合物が混
入し、これによりVRの低下が起る。これら金属
イオン等の混入を完全に防止する事は現実に極め
て困難である。
本発明者らは、上記金属イオン等を捕捉し、そ
の影響力を無くすことにより、PVCのVRを向上
させる方法を鋭意検討した結果、ジシクロペンタ
ジエンと無水マレイン酸の共重合体（以下Ｄ−Ｍ
コポリマーと略称する）を特定量添加する事によ
り得られたPVC組成物のVRが向上する事を見い
出し本発明に到つた。
本発明は、Ｄ−ＭコポリマーをPVC当り0.005
〜５重量％添加する事を特徴とするVRの大きい
PVCの組成物である。
本発明で言うPVCとは、塩化ビニルホモポリ
マーの外に塩化ビニルと共重合可能な単量体、例
えばエチレン、プロピレン、酢酸ビニル、プロピ
オン酸ビニル、アクリル酸、アクリル酸エステ
ル、ビニルエーテル類、その他種々の公知の共重
合可能な単量体と塩化ビニルの共重合体および塩
化ビニルを主成分とするグラフト共重合体を含
み、懸濁重合、乳化重合、塊状重合、気相重合等
公知の重合法のいづれの方法によつて得られたも
のでも使用し得る。
本発明で使用するＤ−Ｍコポリマーの分子量
は、特に範囲を限定するものではないが、実用上
1000〜20000程度のものが好ましい。Ｄ−Ｍコポ
リマーのジシクロペンタジエンと無水マレイン酸
の共重合比はジシクロペンタジエン１モルに対
し、無水マレイン酸１〜２モルであり、酸価は
100以上である事が好ましい。
Ｄ−Ｍコポリマーはジシクロペンタジエン、無
水マレイン酸、溶剤、触媒を反応器に入れて撹拌
しながら加熱し、反応終了後溶剤及び未反応物を
分離して得ることができる。
Ｄ−Ｍコポリマーの添加量は多い程VR向上効
果が大きくなるが、PVCに対し５重量％を超え
ると他の物性への影響が大きくなる為実用的でな
い。また、0.005重量％以下ではほとんどVR改良
効果が認められない。
Ｄ−ＭコポリマーをPVCに添加する時期は、
PVCの重合前、重合中、重合終了時あるいは成
形加工時いずれでも良いが、成形加工時よりも重
合時に添加する同一添加量ではVR向上効果が大
きい傾向がみられる。
PVCにＤ−Ｍコポリマーを添加し、成形加工
するに当つては常法に従つて可塑剤、滑剤、安定
剤、着色剤等を配合して均一混合し、押出成形
機、カレンダーロール、射出成形機等により成形
する。
次に実例をあげて本発明の組成物を更に具体的
に説明する。
実施例 １
ａ ６m2反応器に純水3000Kg、塩化ビニルモノマ
ー2000Kg、ターシヤリブチルパーオキシネオデ
カネート0.6Kg、水溶性ポリビニルアルコール
1.6Kgを入れ、撹拌しながら57℃に加熱した。
重合は圧力が1.0Kg／cm2低下するまで行い、約
80％の転化率を得た。
得られた生成物100部、DOP50部、三塩基性
硫酸鉛５部を混合し、150℃に加熱したロール
で10分間混練した後、170℃で５分間プレスし
て約1.0mm厚のシートを作成した。このシート
のVRをJIS−Ｋ−6723に準じた方法で測定し
比較のデータとした。
ｂ 分子量8000、酸価250のＤ−Ｍコポリマーを、
重合開始前に塩化ビニルモノマー当り0.005重
量％添加する点を除いてａと同様に行つた。
ｃ ｂに記したＤ−Ｍコポリマーを重合開始前に
塩化ビニルモノマー当り0.005重量％添加する
点を除いてａと同様に行つた。
ｄ ｂに記したＤ−Ｍコポリマーを重合終了時に
塩化ビニルモノマー当り0.005重量％添加する
点を除いてａと同様に行つた。
Ｄ−Ｍコポリマーは下記処方によりジシクロペ
ンタジエン、無水マレイン酸、溶剤、触媒を反応
器に入れて撹拌しながら加熱し、反応終了後溶剤
及び未反応物を分離して得た。
The present invention relates to a composition that improves the volume resistivity (hereinafter abbreviated as VR) of a vinyl chloride resin (hereinafter abbreviated as PVC). Originally, PVC is a plastic with a high volume resistivity and is used as an electrical insulating material. This causes a decrease in VR. In reality, it is extremely difficult to completely prevent the contamination of these metal ions. The present inventors have intensively investigated a method for improving the VR of PVC by capturing the metal ions and eliminating their influence. As a result, the present inventors have developed a copolymer (hereinafter referred to as D- M
The inventors have discovered that the VR of the resulting PVC composition can be improved by adding a specific amount of a copolymer. The present invention uses D-M copolymer at 0.005% per PVC.
Large VR characterized by adding ~5% by weight
It is a composition of PVC. In the present invention, PVC refers to monomers copolymerizable with vinyl chloride in addition to vinyl chloride homopolymers, such as ethylene, propylene, vinyl acetate, vinyl propionate, acrylic acid, acrylic esters, vinyl ethers, and other various monomers. Copolymers of vinyl chloride and known copolymerizable monomers, and graft copolymers containing vinyl chloride as a main component, and known polymerization methods such as suspension polymerization, emulsion polymerization, bulk polymerization, and gas phase polymerization. Those obtained by either method can be used. Although the molecular weight of the D-M copolymer used in the present invention is not particularly limited, it is practically
A value of about 1000 to 20000 is preferable. The copolymerization ratio of dicyclopentadiene and maleic anhydride in the D-M copolymer is 1 to 2 mol of maleic anhydride per 1 mol of dicyclopentadiene, and the acid value is
It is preferable that it is 100 or more. The DM copolymer can be obtained by placing dicyclopentadiene, maleic anhydride, a solvent, and a catalyst in a reactor, heating it while stirring, and separating the solvent and unreacted materials after the reaction is completed. The larger the amount of D-M copolymer added, the greater the effect of improving VR, but if it exceeds 5% by weight based on PVC, it is not practical because it has a large influence on other physical properties. In addition, at 0.005% by weight or less, almost no VR improvement effect is observed. When should D-M copolymer be added to PVC?
It may be added before, during, after polymerization, or during molding of PVC, but the effect of improving VR tends to be greater when the same amount is added during polymerization than during molding. When adding D-M copolymer to PVC and molding it, plasticizers, lubricants, stabilizers, coloring agents, etc. are mixed uniformly according to conventional methods, and the process is carried out using an extrusion molding machine, a calendar roll, and injection molding. Shape using a machine, etc. Next, the composition of the present invention will be explained in more detail by giving examples. Example 1 a In a 6 m 2 reactor, 3000 kg of pure water, 2000 kg of vinyl chloride monomer, 0.6 kg of tertiary butyl peroxyneodecanate, and water-soluble polyvinyl alcohol
1.6 kg was added and heated to 57°C while stirring.
Polymerization was carried out until the pressure decreased by 1.0Kg/ cm2 , approximately
A conversion rate of 80% was obtained. 100 parts of the obtained product, 50 parts of DOP, and 5 parts of tribasic lead sulfate were mixed, kneaded for 10 minutes with a roll heated to 150°C, and then pressed for 5 minutes at 170°C to form a sheet with a thickness of about 1.0 mm. Created. The VR of this sheet was measured in accordance with JIS-K-6723 and used as data for comparison. b A D-M copolymer with a molecular weight of 8000 and an acid value of 250,
The same procedure as a was carried out except that 0.005% by weight of vinyl chloride monomer was added before the start of polymerization. c The same procedure as a was carried out except that 0.005% by weight of the DM copolymer described in b was added before the start of the polymerization, based on the vinyl chloride monomer. d The same procedure as a was carried out except that 0.005% by weight of the DM copolymer described in b was added at the end of the polymerization based on the vinyl chloride monomer. The DM copolymer was obtained by placing dicyclopentadiene, maleic anhydride, a solvent, and a catalyst in a reactor and heating with stirring, and after the reaction was completed, the solvent and unreacted materials were separated.
【表】【table】
【表】 実施例１のVR測定結果を表−１に示す。【table】 The VR measurement results of Example 1 are shown in Table-1.
【表】
実施例 ２
ａ 懸濁重合法により得た重合度1000のホモ
PVC100部、DOP50部、三塩基性硫酸鉛５部を
混合し、150℃に加熱したロールで10分間混練
した後、170℃で５分間プレスして約1.0mm厚の
シートを作成した。このシートのVRを、JIS
−Ｋ−6723に準じた方法で測定し比較のデータ
とした。
ｂ 分子量20000、酸価230のＤ−Ｍコポリマーを
表−２に記した割合で添加する点を除いてａと
同様に行つた。
Ｄ−Ｍコポリマーは下記処分により得た。[Table] Example 2 a Homo with a degree of polymerization of 1000 obtained by suspension polymerization method
100 parts of PVC, 50 parts of DOP, and 5 parts of tribasic lead sulfate were mixed, kneaded for 10 minutes using rolls heated to 150°C, and then pressed for 5 minutes at 170°C to create a sheet with a thickness of about 1.0 mm. VR of this sheet, JIS
- Measured using a method similar to K-6723 and used as data for comparison. b The same procedure as a was carried out except that a DM copolymer having a molecular weight of 20,000 and an acid value of 230 was added in the proportions shown in Table 2. The DM copolymer was obtained by the following procedure.
【表】 実施例２のVR測定結果を表−２に示す。【table】 The VR measurement results of Example 2 are shown in Table-2.
Claims (1)
ロペンタジエンと無水マレイン酸の共重合体
0.005〜５重量％とから成る塩化ビニル系樹脂組
成物。1 Copolymer of 99.995 to 95% by weight of vinyl chloride resin, dicyclopentadiene, and maleic anhydride
A vinyl chloride resin composition comprising 0.005 to 5% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11294883A JPS606741A (en) | 1983-06-24 | 1983-06-24 | Vinyl chloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11294883A JPS606741A (en) | 1983-06-24 | 1983-06-24 | Vinyl chloride resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS606741A JPS606741A (en) | 1985-01-14 |
| JPH035422B2 true JPH035422B2 (en) | 1991-01-25 |
Family
ID=14599523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11294883A Granted JPS606741A (en) | 1983-06-24 | 1983-06-24 | Vinyl chloride resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS606741A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62149742A (en) * | 1985-12-25 | 1987-07-03 | Toyo Soda Mfg Co Ltd | Vinyl chloride polymer composition |
-
1983
- 1983-06-24 JP JP11294883A patent/JPS606741A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS606741A (en) | 1985-01-14 |
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