JPH06199951A - Polymerization of vinyl chloride monomer - Google Patents
Polymerization of vinyl chloride monomerInfo
- Publication number
- JPH06199951A JPH06199951A JP27792092A JP27792092A JPH06199951A JP H06199951 A JPH06199951 A JP H06199951A JP 27792092 A JP27792092 A JP 27792092A JP 27792092 A JP27792092 A JP 27792092A JP H06199951 A JPH06199951 A JP H06199951A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- vinyl chloride
- life temperature
- polymerization rate
- polymer
- 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.)
- Pending
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 title claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 title abstract description 55
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 18
- -1 peroxy ester Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 8
- CRJIYMRJTJWVLU-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yl 3-(5,5-dimethylhexyl)dioxirane-3-carboxylate Chemical compound CC(C)(C)CCCCC1(C(=O)OC(C)(C)CC(C)(C)C)OO1 CRJIYMRJTJWVLU-UHFFFAOYSA-N 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 2
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 2
- 239000010935 stainless steel Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 abstract 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 11
- 239000003999 initiator Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000004040 coloring Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- YPIFGDQKSSMYHQ-UHFFFAOYSA-M 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC([O-])=O YPIFGDQKSSMYHQ-UHFFFAOYSA-M 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- GGSRTHRSSCWGGK-UHFFFAOYSA-L 2,2-dibutyl-5-hydroxy-1,3,2-dioxastannepane-4,7-dione Chemical compound CCCC[Sn]1(CCCC)OC(=O)CC(O)C(=O)O1 GGSRTHRSSCWGGK-UHFFFAOYSA-L 0.000 description 1
- JQZZYFIUKZLQDV-UHFFFAOYSA-N 2-(2,3-dimethylbutan-2-yl)-10,10-dimethylundecaneperoxoic acid Chemical compound CC(C)C(C)(C)C(C(=O)OO)CCCCCCCC(C)(C)C JQZZYFIUKZLQDV-UHFFFAOYSA-N 0.000 description 1
- QBEGGJJJXMLJSU-UHFFFAOYSA-N 2-(2,3-dimethylbutan-2-yl)-7,7-dimethyloctaneperoxoic acid Chemical compound CC(C)C(C)(C)C(C(=O)OO)CCCCC(C)(C)C QBEGGJJJXMLJSU-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- DTGWMJJKPLJKQD-UHFFFAOYSA-N butyl 2,2-dimethylpropaneperoxoate Chemical group CCCCOOC(=O)C(C)(C)C DTGWMJJKPLJKQD-UHFFFAOYSA-N 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
- 239000003054 catalyst Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 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
- 238000004904 shortening Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は（Ａ）ジー１ーメチルヘ
プチルペルオキシジカーボネートと（Ｂ）１０時間半減
期温度４２〜３０℃の範囲にあるペルオキシエステルを
併用で重合開始剤として使用し、塩化ビニルの重合体、
又はこれと共重合しうる単量体との共重合体を製造する
際、重合開始剤の使用量が少なくて重合時間が短縮で
き、重合末期での重合速度低下がなく、加工時臭気が少
なく、しかも加工製品の色相も改善される塩化ビニル重
合体の重合方法に関する。The present invention uses (A) di-1-methylheptyl peroxydicarbonate and (B) a peroxyester having a 10-hour half-life temperature in the range of 42 to 30 ° C. in combination as a polymerization initiator, Vinyl chloride polymer,
Alternatively, when producing a copolymer with a monomer copolymerizable with this, the amount of the polymerization initiator used is small and the polymerization time can be shortened, there is no decrease in the polymerization rate at the end of the polymerization, and there is little odor during processing. Moreover, the present invention relates to a method for polymerizing a vinyl chloride polymer in which the hue of processed products is improved.
【０００２】[0002]
【従来の技術】塩化ビニル製造メーカーに於ては汎用樹
脂の生産性の向上のため、重合時間の短縮できる有機過
酸化物が求められている。 例えば、ジイソプロピルペ
ルオキシジカーボネート、ジ−２−エチルヘキシルペル
オキシジカーボネート等のジアルキルペルオキシジカー
ボネート類（１０時間半減期温度４０〜４５℃）は塩化
ビニルの重合開始剤として使用されるが、重合の後半で
重合速度が落ち、高重合率で樹脂が得られない。 ここ
で言う１０時間半減期温度とはペルオキサイドの濃度が
１０時間で半分になる温度を言い、分解の速さの目安と
なる。 以下１０時間半減期温度を半減期温度と略す。2. Description of the Related Art Manufacturers of vinyl chloride are demanding organic peroxides which can reduce the polymerization time in order to improve the productivity of general-purpose resins. For example, dialkyl peroxydicarbonates such as diisopropyl peroxy dicarbonate and di-2-ethylhexyl peroxy dicarbonate (10-hour half-life temperature 40 to 45 ° C.) are used as a polymerization initiator of vinyl chloride, but in the latter half of the polymerization, Polymerization rate slows down, and a resin cannot be obtained with a high polymerization rate. The 10-hour half-life temperature referred to here is the temperature at which the concentration of peroxide halves in 10 hours, and is a measure of the decomposition rate. Hereinafter, the 10-hour half-life temperature is abbreviated as the half-life temperature.
【０００３】また従来より使用されてきたターシャリー
ブチルペルオキシピバレート、ターシャリーブチルペル
オキシネオデカノエート等のペルオキシエステル類は半
減期温度が高く短時間では高重合率が得られない。 ま
た、加水分解性があり重合効率がよくない。Further, peroxyesters such as tertiary butyl peroxypivalate and tertiary butyl peroxyneodecanoate which have been used conventionally have a high half-life temperature and a high polymerization rate cannot be obtained in a short time. Also, it is hydrolyzable and the polymerization efficiency is not good.
【０００４】一方、クミルペルオキシネオデカノエート
は半減期温度が３８℃と低いため、重合時間を短縮する
のに使用されるが、重合体の加工時にアセトフェノンや
フェーノールに近い分解物の臭気が強いと言う欠点があ
る。On the other hand, cumyl peroxyneodecanoate has a low half-life temperature of 38 ° C. and is therefore used for shortening the polymerization time, but the odor of decomposed products close to acetophenone and phenol during processing of the polymer is It has the drawback of being strong.
【０００５】これらの改良のためこれまで種々工夫がこ
らされてきた。 例えば特公昭５８−１２０６１３公報
ではターシャリーオクチルペルオキシネオデカノエート
を使用した重合体では加工時に臭気のない塩化ビニル重
合体を得られることが提案されている。 しかし、この
重合開始剤は多量に使用しないと重合が完結しないとい
う欠点がある。Various improvements have been made so far for these improvements. For example, Japanese Examined Patent Publication (Kokoku) No. 58-120613 proposes that a polymer using tertiary octyl peroxy neodecanoate can give a vinyl chloride polymer having no odor during processing. However, there is a drawback that the polymerization is not completed unless a large amount of this polymerization initiator is used.
【０００６】また、ターシャリーオクチルパルオキシネ
オデカノエートを使用し重合を短時間で完結させるため
多量に使用すると、ターシャリーオクチルパルオキシネ
オデカノエートの分解物から起因する臭気がある。When tertiary octyl paroxy neodecanoate is used in a large amount in order to complete the polymerization in a short time, there is an odor caused by the decomposition product of tertiary octyl paroxy neodecanoate.
【０００７】他に、特公昭６０−３０８６公報では、ジ
ー１ーメチルヘプチルペルオキシジカーボネートを使用
した場合、樹脂の熱安定性が優れており、触媒の持続性
が優れている、すなわち重合後半で重合速度が低下しな
いということが提案されている。 しかしながら、ジー
１ーメチルヘプチルペルオキシジカーボネートは所定の
重合率を得るには、重合時間が１０時間ぐらい掛かり、
現在ではさらなる重合サイクルの短縮をするが要望さ
れ、その目的をはたすためには、開始剤を多量に使用し
なくてはならない。In addition, in JP-B-60-3086, when di-1-methylheptylperoxydicarbonate is used, the thermal stability of the resin is excellent and the durability of the catalyst is excellent, that is, in the latter half of the polymerization. It is proposed that the polymerization rate does not decrease. However, di-methylheptyl peroxydicarbonate takes about 10 hours to obtain a predetermined polymerization rate,
At present, it is desired to further shorten the polymerization cycle, and in order to achieve the purpose, a large amount of initiator must be used.
【０００８】また生産性の向上では、重合速度を一定に
するために半減期温度の低い開始剤と半減期温度の高い
開始剤を組合せて重合速度を均一にし生産性を向上する
方法が提案されている。例えば、特公昭４６−１４６７
０公報では半減期温度の低い開始剤としてアセチルシク
ロヘキシルスルホニルペルオキシドと半減期温度の高い
開始剤としてジアルキルペルオキシジカーボネートの組
合せが使用されている。 しかしながらアセチルシクロ
ヘキシルスルホニルペルオキシドを多量に使用すると塩
化ビニルの熱安定生が悪くなる。In order to improve the productivity, a method has been proposed in which an initiator having a low half-life temperature and an initiator having a high half-life temperature are combined to make the polymerization rate uniform so that the polymerization rate is constant. ing. For example, Japanese Patent Publication No. 46-1467
In JP-A-0, the combination of acetylcyclohexylsulfonyl peroxide as an initiator having a low half-life temperature and a dialkyl peroxydicarbonate as an initiator having a high half-life temperature is used. However, when a large amount of acetylcyclohexylsulfonyl peroxide is used, the heat stability of vinyl chloride deteriorates.
【０００９】また、熱安定性の改良として特開昭５６−
１４９４０７公報ではクミルペルオキシネオデカノエー
トとジアルキルペルオキシジカーボネート例えばジ−２
−エチルヘキシルペルオキシジカーボネートの組合せが
使用されている。 しかしこの組合せの場合は、前述の
様にクミルペルオキシネオデカノエートを使用すると可
塑剤等を添加し混練りして加工製品を製造する際、クミ
ルペルオキシネオデカノエート分解物の独特の臭気があ
り、さらに重合後半での重合速度の低下がある。Further, as an improvement in thermal stability, JP-A-56-
In 149407 publication, cumyl peroxyneodecanoate and dialkyl peroxydicarbonates such as di-2
A combination of -ethylhexyl peroxydicarbonate has been used. However, in the case of this combination, when cumyl peroxy neodecanoate is used as described above, when a processed product is manufactured by adding a plasticizer and the like and kneading, the unique characteristic of the decomposed product of cumyl peroxy neodecanoate is There is an odor and there is a decrease in the polymerization rate in the latter half of the polymerization.
【００１０】[0010]
【発明が解決しようとする問題点】本発明の目的は重合
開始剤の使用量が少なくて重合時間が短縮でき、重合末
期での重合速度の低下がなく、高重合率で樹脂が得ら
れ、しかも重合によりえられた樹脂を可塑剤等を添加し
混練りして加工製品を製造する際、有機過酸化物の分解
物による臭気が少なく、加工製品の色相も改善される重
合開始剤を使用した重合方法を提案することである。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The object of the present invention is to use a small amount of a polymerization initiator to shorten the polymerization time, to obtain a resin with a high polymerization rate without lowering the polymerization rate at the end of polymerization. In addition, when a processed product is manufactured by kneading the resin obtained by polymerization with a plasticizer, etc., use a polymerization initiator that produces less odor due to decomposition products of organic peroxides and improves the hue of the processed product. It is to propose the polymerization method.
【００１１】[0011]
【問題点を解決するための手段】本発明者らは、上記課
題を解決するため種々の有機過酸化物を使用し、塩化ビ
ニル系単量体の重合方法について鋭意検討した結果、
（Ａ）ジー１ーメチルヘプチルペルオキシジカーボネー
トと（Ｂ）１０時間半減期温度４２〜３０℃の範囲にあ
るペルオキシエステルを併用で重合開始剤として使用す
ることを特徴とする塩化ビニル系単量体の重合方法を見
出し、本発明を完成した。 すなわち、（Ａ）ジー１ー
メチルヘプチルペルオキシジカーボネートと（Ｂ）１０
時間半減期温度４２〜３０℃の範囲にあるペルオキシエ
ステルを併用することにより、重合速度が一定でかつ、
重合末期で重合速度の低下がなく短時間で重合を完結す
ることを見出した。Means for Solving the Problems The inventors of the present invention have conducted extensive studies on a method for polymerizing vinyl chloride-based monomers using various organic peroxides in order to solve the above problems.
(A) Di-1-methylheptyl peroxydicarbonate and (B) a peroxy ester having a 10-hour half-life temperature in the range of 42 to 30 ° C. are used in combination as a polymerization initiator. The present invention was completed by finding out the polymerization method of. That is, (A) di-1-methylheptyl peroxydicarbonate and (B) 10
By using the peroxy ester in the range of the time half-life temperature of 42 to 30 ° C. in combination, the polymerization rate is constant and
It was found that the polymerization rate did not decrease at the end of the polymerization and the polymerization was completed in a short time.
【００１２】本発明において塩化ビニル系単量体の重合
時の一般的な重合開始剤の使用量は塩化ビニル１００重
量部当り０．００５〜０．５重量部である。 ０．００
５重量部未満では重合速度が極めて遅くなり、また０．
５重量部を越えると重合反応が急激に起こり、温度制御
が困難となる。In the present invention, the general amount of the polymerization initiator used during the polymerization of the vinyl chloride monomer is 0.005 to 0.5 part by weight per 100 parts by weight of vinyl chloride. 0.00
If it is less than 5 parts by weight, the polymerization rate will be extremely slow, and the polymerization rate will be 0.
If it exceeds 5 parts by weight, the polymerization reaction will occur rapidly, making temperature control difficult.
【００１３】本発明において（Ａ）ジー１ーメチルヘプ
チルペルオキシジカーボネートと（Ｂ）１０時間半減期
温度４２〜３０℃の範囲にあるペルオキシエステルの混
合割合を０．１〜１０．０の範囲で使用される。 この
範囲外の場合は、本発明の目的を達成することが難しく
なる。In the present invention, the mixing ratio of (A) di-1-methylheptyl peroxydicarbonate and (B) peroxyester having a 10-hour half-life temperature in the range of 42 to 30 ° C. is in the range of 0.1 to 10.0. used. Outside this range, it becomes difficult to achieve the object of the present invention.
【００１４】本発明における塩化ビニル系単量体の重合
には共重合可能な他のビニル単量体、例えばエチレン、
酢酸ビニル、塩化ビニリデン、スチレン、アクリル酸エ
ステル類等との共重合も含まれる。For the polymerization of the vinyl chloride-based monomer in the present invention, another copolymerizable vinyl monomer such as ethylene,
Copolymerization with vinyl acetate, vinylidene chloride, styrene, acrylic acid esters and the like is also included.
【００１５】また、１０時間半減期温度４２〜３０℃の
範囲にあるペルオキシエステルとして、例えば、ターシ
ャリーオクチルペルオキシネオデカノエート、クミルペ
ルオキシネオデカノエート、ターシャリーオクチルペル
オキシネオトリデカノエート、１，１，２−トリメチル
プロピルペルオキシネオデカノエート、クミルペルオキ
シネオトリデカノエート、１，１，２−トリメチルプロ
ピルペルオキシネオトリデカノエート等のが例示され
る。As the peroxyester having a 10-hour half-life temperature of 42 to 30 ° C., for example, tertiary octyl peroxy neodecanoate, cumyl peroxy neodecanoate, tertiary octyl peroxy neotridecanoate, Examples thereof include 1,1,2-trimethylpropylperoxyneodecanoate, cumylperoxyneotridecanoate, and 1,1,2-trimethylpropylperoxyneotridecanoate.
【００１６】半減期温度が４２℃より高いものの場合に
は、少ない開始剤量で重合時間を短縮するのは難しい。
また、半減期温度が３０℃より低いものの場合には重
合速度が均一になりにくい。When the half-life temperature is higher than 42 ° C., it is difficult to shorten the polymerization time with a small amount of the initiator.
Further, when the half-life temperature is lower than 30 ° C., it is difficult to make the polymerization rate uniform.
【００１７】[0017]
【実施例】以下に実施例により本発明の方法をさらに詳
細に説明する。 但し、本発明は実施例に限定されるも
のではない。The method of the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the examples.
【００１８】[0018]
【実施例１】攪拌機を有する５ｌのステンレス製のオー
トクレーブ中に、部分ケン化ポリビニルアルコールを１
ｇとイオン交換水３０００ｇを仕込みよく攪拌し溶解す
る。系内を充分窒素置換しジー１ーメチルヘプチルペル
オキシジカーボネート０．４１６ｇ、１，１，３，３ー
テトラメチルブチルペルオキシネオデカノエート０．３
６１ｇを溶解した１５００ｇの塩化ビニル単量体を圧入
した。攪拌しながら、内温を５７℃にして重合した。
４時間で内圧は平衡圧より４．５ｋｇ/ｃｍ2低下した。
この時点で生成した塩化ビニルを慮過、洗浄し４０〜
５０℃で真空乾燥した。 重合率は９１．８％であっ
た。Example 1 A partially saponified polyvinyl alcohol was added to a 1-liter stainless steel autoclave equipped with a stirrer.
g and ion-exchanged water 3000 g are charged and well stirred to dissolve. The system was thoroughly replaced with nitrogen, and 0.416 g of di-1-methylheptyl peroxydicarbonate and 0.36 of 1,1,3,3-tetramethylbutyl peroxy neodecanoate were added.
1500 g of vinyl chloride monomer in which 61 g was dissolved was pressed in. While stirring, the internal temperature was adjusted to 57 ° C. and the polymerization was carried out.
The internal pressure decreased by 4.5 kg / cm 2 from the equilibrium pressure in 4 hours.
The vinyl chloride produced at this point was carefully washed and washed with 40-
It was vacuum dried at 50 ° C. The polymerization rate was 91.8%.
【００１９】得られた塩化ビニルを用いて初期着色試験
を行なった。 同時に臭気につい調べた。 結果は表１
に示す。An initial coloring test was conducted using the obtained vinyl chloride. At the same time, I investigated the odor. The results are shown in Table 1.
Shown in.
【００２０】［初期着色試験］塩化ビニル１００にジオ
クチルフタレート５０ｇジブチルスズマレート２．５ｇ
を混合し１６０℃で７分間混練し、シートの着色具合を
目視で観察した。[Initial color test] 100 g of vinyl chloride, 50 g of dioctyl phthalate and 2.5 g of dibutyl tin malate
Were mixed and kneaded at 160 ° C. for 7 minutes, and the coloring of the sheet was visually observed.
【００２１】［臭気試験］初期着色試験で出来たシート
の臭気を調べた。[Odor test] The odor of the sheet produced in the initial coloring test was examined.
【００２２】[0022]
【実施例２】実施例１の重合開始剤をジー１ーメチルヘ
プチルペルオキシジカーボネート０．４１６ｇとクミル
ペルオキシネオデカノエート０．３６７ｇに変える以外
は実施例１に準じて重合を行なった。Example 2 Polymerization was carried out in the same manner as in Example 1 except that the polymerization initiator in Example 1 was changed to 0.416 g of di-1-methylheptyl peroxydicarbonate and 0.367 g of cumyl peroxy neodecanoate.
【００２３】[0023]
【比較例１】実施例１の重合開始剤をクミルペルオキシ
ネオデカノエート０．７３６ｇに変える以外は実施例１
に準じて重合を行なった。Comparative Example 1 Example 1 except that the polymerization initiator of Example 1 was changed to 0.736 g of cumyl peroxyneodecanoate.
Polymerization was carried out according to.
【００２４】[0024]
【比較例２】実施例１の重合開始剤を１，１，３，３ー
テトラメチルブチルペルオキシネオデカノエート０．３
６１ｇとジ−２−エチルヘキシルペルオキシジカーボネ
ート０．４１６ｇに変える以外は実施例１に準じて塩化
ビニルの重合を行なった。[Comparative Example 2] The polymerization initiator of Example 1 was replaced by 0.3% of 1,1,3,3-tetramethylbutylperoxyneodecanoate.
Vinyl chloride was polymerized in the same manner as in Example 1 except that 61 g and 0.416 g of di-2-ethylhexyl peroxydicarbonate were used.
【００２５】[0025]
【比較例３】実施例１の重合開始剤をクミルペルオキシ
ネオデカノエート０．３６８ｇとジ−２−エチルヘキシ
ルペルオキシジカーボネート０．４１６ｇに変える以外
は実施例１に準じて塩化ビニルの重合を行なった。[Comparative Example 3] Polymerization of vinyl chloride was carried out in the same manner as in Example 1 except that 0.368 g of cumylperoxyneodecanoate and 0.416 g of di-2-ethylhexylperoxydicarbonate were used as the polymerization initiators of Example 1. I did.
【００２６】[0026]
【比較例４】実施例１の重合開始剤をジー１ーメチルヘ
プチルペルオキシジカーボネート０．８３２ｇに変える
以外は実施例１に準じて塩化ビニルの重合を行なった。Comparative Example 4 Vinyl chloride was polymerized according to Example 1 except that the polymerization initiator of Example 1 was changed to 0.832 g of di-1-methylheptyl peroxydicarbonate.
【００２７】[0027]
【比較例５】実施例１の重合開始剤を１，１，３，３ー
テトラメチルブチルペルオキシネオデカノエート０．７
２１ｇに変える以外は実施例１に準じて塩化ビニルの重
合を行なった。Comparative Example 5 1,1,3,3-tetramethylbutylperoxy neodecanoate 0.7 was added to the polymerization initiator of Example 1.
Polymerization of vinyl chloride was carried out according to Example 1 except that the amount was changed to 21 g.
【００２８】以上の結果を表１に示す。 その表より公
知の開始剤の組合せでは生産性が悪いかまたは熱安定生
や臭気の点で問題があったが、本発明の混合開始剤の場
合はその両者が改良されていることが分かる。The above results are shown in Table 1. It can be seen from the table that the known combinations of initiators have poor productivity or have problems in terms of heat stability and odor, but in the case of the mixed initiator of the present invention, both are improved.
【００２９】[0029]
【発明の効果】本発明の併用系重合開始剤を使用すれ
ば、重合速度が一定化され重合末期での重合速度の低下
がなくなると共に重合時間の短縮がはかれる。EFFECTS OF THE INVENTION By using the combined polymerization initiator of the present invention, the polymerization rate is kept constant, the decrease in the polymerization rate at the final stage of the polymerization is eliminated, and the polymerization time is shortened.
【表１】 [Table 1]
Claims (1)
シジカーボネートと（Ｂ）１０時間半減期温度４２〜３
０℃の範囲にあるペルオキシエステルを併用で重合開始
剤として使用することを特徴とする塩化ビニル系単量体
の重合方法。1. A di-methylheptyl peroxydicarbonate (A) and a 10-hour half-life temperature of 42 to 3 (B).
A method for polymerizing a vinyl chloride-based monomer, which comprises using a peroxy ester in the range of 0 ° C. in combination as a polymerization initiator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27792092A JPH06199951A (en) | 1992-09-22 | 1992-09-22 | Polymerization of vinyl chloride monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27792092A JPH06199951A (en) | 1992-09-22 | 1992-09-22 | Polymerization of vinyl chloride monomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06199951A true JPH06199951A (en) | 1994-07-19 |
Family
ID=17590134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27792092A Pending JPH06199951A (en) | 1992-09-22 | 1992-09-22 | Polymerization of vinyl chloride monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06199951A (en) |
-
1992
- 1992-09-22 JP JP27792092A patent/JPH06199951A/en active Pending
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