JPH04331208A - Production of chlorinated polyolefin - Google Patents
Production of chlorinated polyolefinInfo
- Publication number
- JPH04331208A JPH04331208A JP11398391A JP11398391A JPH04331208A JP H04331208 A JPH04331208 A JP H04331208A JP 11398391 A JP11398391 A JP 11398391A JP 11398391 A JP11398391 A JP 11398391A JP H04331208 A JPH04331208 A JP H04331208A
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin
- weight
- tetrachlorethylene
- chlorine
- chlorination
- 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
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- -1 nitrogenous heterocyclic amine Chemical class 0.000 claims abstract description 39
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229950011008 tetrachloroethylene Drugs 0.000 claims abstract description 30
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000460 chlorine Substances 0.000 claims abstract description 22
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 22
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004090 dissolution Methods 0.000 claims abstract description 5
- ZMGMDXCADSRNCX-UHFFFAOYSA-N 5,6-dihydroxy-1,3-diazepan-2-one Chemical compound OC1CNC(=O)NCC1O ZMGMDXCADSRNCX-UHFFFAOYSA-N 0.000 claims abstract description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims abstract 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000005660 chlorination reaction Methods 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 abstract description 15
- 229920001155 polypropylene Polymers 0.000 abstract description 15
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001412 amines Chemical class 0.000 abstract description 4
- 239000004342 Benzoyl peroxide Substances 0.000 abstract description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011953 free-radical catalyst Substances 0.000 abstract 2
- 238000000034 method Methods 0.000 description 16
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 14
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 150000003567 thiocyanates Chemical class 0.000 description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000013877 carbamide Nutrition 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- UZXXRFKXXJEKJA-UHFFFAOYSA-N 1-ethyl-3-methylimidazolidin-2-one Chemical compound CCN1CCN(C)C1=O UZXXRFKXXJEKJA-UHFFFAOYSA-N 0.000 description 1
- RXRJFXGYBHBKBJ-UHFFFAOYSA-N 1-sulfanylimidazolidine Chemical compound SN1CCNC1 RXRJFXGYBHBKBJ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明はポリオレフィン系素材の
塗装におけるプライマ−、塗料のビヒクル、コ−ティン
剤、接着剤、印刷インキのバインダ−等に使用される塩
素化ポリオレフィンの製造法に関し、従来使用されてい
たオゾン層破壊の恐れのある四塩化炭素溶剤を使用する
ことなく、テトラクロルエチレンを使用するポリオレフ
ィンのオゾン層破壊の恐れのない工業的に実用性のある
簡便な塩素化ポリオレフィンの製造法に関するものであ
る。[Field of Industrial Application] The present invention relates to a method for producing chlorinated polyolefins used as primers, paint vehicles, coating agents, adhesives, binders for printing inks, etc. in coating polyolefin materials. Production of industrially practical and simple chlorinated polyolefin without the risk of ozone layer depletion using tetrachlorethylene without using the previously used carbon tetrachloride solvent that has the risk of ozone layer depletion. It is about law.
【0002】0002
【従来の技術】従来ポリオレフィンの塩素化方法として
は多くの方法がある。工業的に有用な方法としては、BACKGROUND OF THE INVENTION There are many conventional methods for chlorinating polyolefins. As an industrially useful method,
【
0003】四塩化炭素等の有機溶剤にポリオレフィンを
加熱溶解して塩素化する方法(有機溶剤法という)。[
A method of chlorinating polyolefin by heating and dissolving it in an organic solvent such as carbon tetrachloride (referred to as an organic solvent method).
【0004】少量の有機溶剤にポリオレフィンを溶解し
、之を水に分散させるか、或は微粒子のポリオレフィン
を水に直接分散させて塩素化する方法(水懸濁法という
)。(USP3281384 、特開昭47−1378
0 号)[0004] A method of dissolving polyolefin in a small amount of organic solvent and dispersing it in water, or directly dispersing fine particles of polyolefin in water for chlorination (referred to as water suspension method). (USP3281384, Japanese Patent Publication No. 47-1378
No. 0)
【0005】乾いた粉末或は粒状の固体をガス
状の塩素と反応させてα−オレフィン重合体を製造する
方法(無溶剤法)。(DP.2262535 、特公昭
37−6641号)がある。A method for producing an α-olefin polymer by reacting a dry powder or granular solid with gaseous chlorine (solvent-free method). (DP.2262535, Special Publication No. 37-6641).
【0006】[0006]
【発明が解決しようとする課題】前記の種々な用途に使
用される塩素化ポリオレフィンは10−50%の比較的
低塩素含量の塩素化ポリオレフィンが有効であり、これ
らの用途においてはポリオレフィンのより均一な塩素化
により、溶剤に対して均一に、より容易に溶解すること
が必要であり、この点において前記の方法の中で有機溶
剤法が最も有利な方法である。[Problems to be Solved by the Invention] Chlorinated polyolefins used in the various applications mentioned above are effective with a relatively low chlorine content of 10-50%, and in these applications, it is possible to improve the uniformity of polyolefins. It is necessary to uniformly and more easily dissolve the compound in a solvent by chlorination, and in this respect, the organic solvent method is the most advantageous method among the above-mentioned methods.
【0007】有機溶剤法で塩素化反応時に使用される有
機溶剤としては四塩化炭素、クロロホルム、テトラクロ
ルエチレン、メチルクロロホルム等のハロゲン化低級脂
肪族炭化水素、クロルベンゼン等のハロゲン化芳香族炭
化水素がある。これらの中で塩素に対して本質的に不活
性であるのは四塩化炭素だけであり、その他は置換反応
、付加反応により塩素と反応する。この点からして工業
的に使用されているのは大部分四塩化炭素である。しか
しながら四塩化炭素は地球を取り巻くオゾン層を破壊す
る恐れがあるため、今後国際的に規制され工業的に使用
できなくなる。四塩化炭素以外に溶剤としてテトラクロ
ルエチレンを使用した例が幾つかある。(例えばUSP
.2313499 、BP.826495、特公昭42
−2279。)しかしながらこれらは工業的に実用化さ
れていない。その理由は例えば四塩化炭素等のような塩
素に対して不活性な溶剤をポリオレフィンの塩素化時の
溶剤に使用した場合、 通常塩素化ポリオレフィン塩素
化終了後、 水蒸気蒸留、 ドラムドライヤ−、エクス
トル−ダ−等の方法で塩素化時の溶剤が除去され、固形
品として、又はトルエン、キシレン、ソルベントナフサ
等の溶剤に溶解して使用される。また塩素化時の溶剤は
特別な工程をとらずに回収して再使用される。Organic solvents used in the chlorination reaction in the organic solvent method include carbon tetrachloride, halogenated lower aliphatic hydrocarbons such as chloroform, tetrachloroethylene, and methylchloroform, and halogenated aromatic hydrocarbons such as chlorobenzene. There is. Among these, only carbon tetrachloride is essentially inert to chlorine, and the others react with chlorine through substitution reactions and addition reactions. From this point of view, carbon tetrachloride is mostly used industrially. However, because carbon tetrachloride threatens to destroy the ozone layer surrounding the earth, it will be regulated internationally and will no longer be able to be used industrially. There are several examples of using tetrachlorethylene as a solvent in addition to carbon tetrachloride. (For example, USP
.. 2313499, BP. 826495, special public service 1977
-2279. ) However, these have not been put into practical use industrially. The reason for this is that when a solvent inert to chlorine, such as carbon tetrachloride, is used as a solvent for chlorinating polyolefin, usually after the chlorination of the chlorinated polyolefin is completed, steam distillation, drum dryer, extrusion, etc. The solvent used during chlorination is removed by a method such as a chlorination process, and the product is used as a solid product or dissolved in a solvent such as toluene, xylene, or solvent naphtha. Furthermore, the solvent used during chlorination can be recovered and reused without any special process.
【0008】ところがポリオレフィンの塩素化時の溶剤
にテトラクロルエチレンを使用した場合、従来の塩素化
方法では、ポリオレフィンの塩素化と共に溶剤であるテ
トラクロルエチレンの塩素化も起り、主にヘキサクロル
エタンが多量に生成する。このヘキサクロルエタンは融
点が187 ℃で昇華性があり、強いナフタレン臭があ
る。
これによってテトラクロルエチレンの回収使用を行う場
合には少なくとも蒸留をして再使用をする必要がある。
更に塩素化ポリオレフィンの製品中にヘキサクロルエタ
ン等が残存すると、使用者側において臭気等の環境が問
題になること、また塩素化ポリオレフィンの諸物性への
悪影響を及ぼすため、ヘキサクロルエタンの特別な除去
工程が必要であり、コストが高くつくという問題点があ
る。However, when tetrachlorethylene is used as a solvent during chlorination of polyolefin, in the conventional chlorination method, chlorination of the solvent tetrachlorethylene occurs as well as chlorination of the polyolefin, and mainly hexachloroethane is chlorinated. Produce in large quantities. This hexachloroethane has a melting point of 187°C, sublimes, and has a strong naphthalene odor. Therefore, when recovering and using tetrachlorethylene, it is necessary to at least distill it and reuse it. Furthermore, if hexachloroethane remains in a chlorinated polyolefin product, it will cause environmental problems such as odor for the user, and it will also have an adverse effect on the physical properties of the chlorinated polyolefin. There is a problem that a removal step is required and the cost is high.
【0009】本発明は上記に鑑みポリオレフィンの塩素
化時の溶剤にテトラクロルエチレンを使用した場合、エ
トラクロルエチレンの塩素化がほとんど起こらず、ポリ
オレフィンのみが塩素化される工業的に実用性のある簡
易な方法による塩素化ポリオレフィンの製造方法を提供
することを目的とするものである。In view of the above, the present invention is an industrially practical method in which when tetrachlorethylene is used as a solvent during chlorination of polyolefin, chlorination of etrachlorethylene hardly occurs and only polyolefin is chlorinated. The object of the present invention is to provide a method for producing chlorinated polyolefin using a simple method.
【0010】0010
【課題を解決するための手段】本発明の第1はアルキル
アミン類、アルカノ−ルアミン類及び含窒素複素環式ア
ミン類の一種又は複数種の存在下、ポリオレフィンをテ
トラクロルエチレンに溶解温度以上で溶解し、ついでラ
ジカル触媒の存在下、又は光照射下において、塩素を導
入することによって、テトラクロルエチレンに対する塩
素化を防止しながら、ポリオレフィンのみを塩素化する
塩素化ポリオレフィンの製造であり、その第2は上記ア
ルキルアミン類、アルカノ−ルアミン類及び含窒素複素
環式アミン類の代わりにチオシアン酸塩類を使用する第
1発明記載の塩素化ポリオレィンの製造法であり、その
第3は第1発明のアルキルアミン類、アルカノ−ルアミ
ン類及び含窒素複素環式アミン類の代わりに一般式[Means for Solving the Problems] The first aspect of the present invention is to dissolve a polyolefin in tetrachlorethylene at a temperature higher than its dissolution temperature in the presence of one or more of alkylamines, alkanolamines, and nitrogen-containing heterocyclic amines. This is the production of chlorinated polyolefin in which only the polyolefin is chlorinated while preventing the chlorination of tetrachlorethylene by dissolving it and then introducing chlorine in the presence of a radical catalyst or under light irradiation. 2 is a method for producing a chlorinated polyolein according to the first invention, in which thiocyanates are used in place of the alkylamines, alkanolamines, and nitrogen-containing heterocyclic amines; General formula in place of alkylamines, alkanolamines and nitrogen-containing heterocyclic amines
【化
2】
で表される。(なお一般式It is represented by [Chemical formula 2]. (The general formula
【化2】においてR1 及びR2 はアルキル基、Xは
酸素又は硫黄原子、nは2乃至3の整数を示す)。環式
ウレア、環式チオウレアを使用する第1発明記載の塩素
化ポリオレフィンの製造法に関するものである。(In Formula 2, R1 and R2 are alkyl groups, X is an oxygen or sulfur atom, and n is an integer of 2 to 3). The present invention relates to a method for producing a chlorinated polyolefin according to the first invention using a cyclic urea or a cyclic thiourea.
【0011】[0011]
【化2】[Chemical 2]
【0012】本発明のポリオレフィンはポリプロピレン
、ポリエチレン、エチレン−プロピレン共重合体及びエ
チレン−酢酸ビニル共重合体等のエチレン共重合体、ポ
リプロピレン−ブテン共重合体、ポリイソブチレン、天
然ゴム、オレフィン系ゴム等である。The polyolefins of the present invention include polypropylene, polyethylene, ethylene copolymers such as ethylene-propylene copolymers and ethylene-vinyl acetate copolymers, polypropylene-butene copolymers, polyisobutylene, natural rubber, olefin rubber, etc. It is.
【0013】本発明に使用されるラジカル触媒は通常の
ラジカル生成物質、例えばベンゾイルパ−オキサイド、
ジアルキルパ−オキサイド、ケトンパ−オキサイド、パ
−オキシエステル、ジアルキルパ−オキサイド、パ−カ
−ボネイト等の有機過酸化物、アゾニトリル化合物、ア
ゾアミデイン化合物、シクロアゾアミデイン化合物、ア
ゾアミド化合物、アルキルアゾ化合物等のアゾ系化合物
等がある。またそれらのラジカル触媒の一種又は二種以
上の混合物、又はそれらと光触媒との組合せにより、反
応温度と反応時間とを勘案して選択する必要がある。ラ
ジカル触媒の使用量は使用するポリオレフィンに対して
0.05〜10重量%で、0.05重量%未満ではその
効果がなく、また10重量%を超過して使用するも使用
量に相当する効果は得られない。本発明に使用される光
触媒は自然光、蛍光灯、ケミカルランプ又はUVランプ
等の光で光触媒単独でも又はラジカル触媒との組合せて
もよい。本発明に使用されるアミン類はトリエチルアミ
ン、ジイソプロピルアミン等のアルキルアミン、ピペリ
ジン、N−メチルピペリジン、ピペラジン、ピリジン、
N−メチルピロ−ル、2−ピロリドン、モルホリン等の
含窒素複素環式アミン類及びモノエタノ−ルアミン、イ
ソプロパノ−ルアミン等のアルカノ−ルアミンである。
本発明に使用されるチオシアン酸塩類はチオシアン酸ア
ンモニウム、チオシアン酸ソ−ダ等である。本発明に使
用される環式ウレア及び環式チオウレア類は前記The radical catalyst used in the present invention is a conventional radical generating substance such as benzoyl peroxide,
Organic peroxides such as dialkyl peroxide, ketone peroxide, peroxy ester, dialkyl peroxide, and percarbonate; azo compounds such as azonitrile compounds, azoamideine compounds, cycloazoamideine compounds, azoamide compounds, and alkylazo compounds; There are compounds etc. Further, it is necessary to select one type or a mixture of two or more of these radical catalysts, or a combination of them and a photocatalyst, taking into consideration the reaction temperature and reaction time. The amount of radical catalyst used is 0.05 to 10% by weight based on the polyolefin used. If it is less than 0.05% by weight, there is no effect, and if it is used in excess of 10% by weight, the effect is equivalent to the amount used. cannot be obtained. The photocatalyst used in the present invention may be used alone or in combination with a radical catalyst using light such as natural light, a fluorescent lamp, a chemical lamp, or a UV lamp. The amines used in the present invention include alkyl amines such as triethylamine and diisopropylamine, piperidine, N-methylpiperidine, piperazine, pyridine,
These include nitrogen-containing heterocyclic amines such as N-methylpyrrole, 2-pyrrolidone and morpholine, and alkanolamines such as monoethanolamine and isopropanolamine. The thiocyanates used in the present invention include ammonium thiocyanate and sodium thiocyanate. The cyclic ureas and cyclic thioureas used in the present invention are as described above.
【化2
】に示す一般式で表される環式ウレア、環式チオウレア
で例えば1,3−ジメチル−2−イミダゾリジノン、1
−メチル−3−エチル−2−イミダゾリジノン、1,3
−イミダゾリジン−2−チオン、テトラハライド−1,
3−ジメチル−2ピリジノン等である。[chemical 2
Cyclic urea and thiourea represented by the general formula shown in the formula, such as 1,3-dimethyl-2-imidazolidinone, 1
-Methyl-3-ethyl-2-imidazolidinone, 1,3
-imidazolidine-2-thione, tetrahalide-1,
3-dimethyl-2pyridinone and the like.
【0014】上記アミン類、チオシアン酸塩類、環式ウ
レア、環式チオウレア類はポリオレフィンの塩素化にお
いて、触媒的に働きテトラクロルエチレンに対する塩素
付加反応を抑制する効果がある。これらの使用量は反応
液全体に対して5ppm 〜1重量%、好ましくは20
ppm 〜1000ppm である。5ppm 未満で
はその効果が乏しく、1重量%を超過して使用するも使
用量に相当する効果は得られず、逆に反応液の着色及び
ポリオレフィンに対する塩素の反応性低下を招く恐れが
ある。本発明におけるポリオレフィンの溶解温度は使用
するポリオレフィンの溶解温度以上で行い、特に結晶性
ポリオレフィンでは少なくとも溶解温度の10℃以上の
温度で溶解することが望ましい。充分にポリオレフィン
が溶解しない状態で塩素を通じるとポリオレフィンに対
する塩素の反応性が低下し、そのため不均一な塩素化反
応が起こる。例えばテトラクロルエチレンに対する溶解
温度が約104 ℃であるアイソタクチックポリプロピ
レンの場合、還流下(122 ℃)で1時間過熱撹拌す
ることが望ましい。The above-mentioned amines, thiocyanates, cyclic ureas, and cyclic thioureas act as catalysts in the chlorination of polyolefins, and have the effect of suppressing the chlorine addition reaction to tetrachlorethylene. The amount of these used is 5 ppm to 1% by weight, preferably 20% by weight based on the entire reaction solution.
ppm to 1000 ppm. If it is less than 5 ppm, the effect is poor, and if it is used in excess of 1% by weight, the effect corresponding to the amount used cannot be obtained, and on the contrary, it may cause coloring of the reaction solution and a decrease in the reactivity of chlorine with respect to polyolefin. The melting temperature of the polyolefin in the present invention is preferably higher than the melting temperature of the polyolefin used, and especially crystalline polyolefins are desirably melted at a temperature of at least 10° C. or higher than the melting temperature. If chlorine is passed in a state where the polyolefin is not sufficiently dissolved, the reactivity of chlorine with respect to the polyolefin will be reduced, resulting in a non-uniform chlorination reaction. For example, in the case of isotactic polypropylene whose dissolution temperature in tetrachlorethylene is about 104°C, it is desirable to heat and stir under reflux (122°C) for 1 hour.
【0015】本発明における反応温度は使用するポリオ
レフィンの溶解温度以上で行うことが望ましく、通常は
40〜140 ℃で、140 ℃以上ではポリオレフィ
ンに付加した塩素が脱塩酸反応によって離脱し、着色及
び塩素の反応性低下が著しくなる。また、塩素化が進む
に従って生成する塩素化ポリオレフィンの溶解温度が低
下するので、塩素化が進むに従って徐々に反応温度を下
げたり、或は段階的に反応温度を下げて塩素化すること
も可能である。[0015] The reaction temperature in the present invention is desirably carried out at a temperature higher than the melting temperature of the polyolefin used, usually from 40 to 140°C. At 140°C or higher, chlorine added to the polyolefin is separated by a dehydrochloric acid reaction, resulting in discoloration and chlorine. Reactivity decreases significantly. In addition, as the chlorination progresses, the dissolution temperature of the chlorinated polyolefin that is produced decreases, so it is possible to gradually lower the reaction temperature as the chlorination progresses, or to perform chlorination by lowering the reaction temperature in stages. be.
【0016】[0016]
【実施例1】 105.3 重量部のアイソタクチッ
クポリプロピレン(数平均分子量15000)及び0.
05重量部のチオシアン酸アンモニウムを947.3
重量部のテトラクロルエチレンに添加した。還流下12
2 ℃ 、1時間強撹拌し充分にアイソタクチックポリ
プロピレンを溶解した。溶液温度を105 ℃に下げ、
4.2 重量部のt−ブチル−パ−オキシベンゾエ−ト
を添加し、0.6 重量部/分の速度で135.2重量
部の塩素ガスを導入した。所定量の塩素ガスを導入した
後、5分間同温度で熟成反応を行い室温まで冷却した。
得られた塩素化ポリプロピレン(塩素含有量36.7重
量%)のテトラクロルエチレン溶液についてガスクロマ
トグラフ分析を行った結果ヘキサクロルエタンの生成量
は0.0 重量部であった。Example 1 105.3 parts by weight of isotactic polypropylene (number average molecular weight 15,000) and 0.3 parts by weight of isotactic polypropylene (number average molecular weight 15,000).
05 parts by weight of ammonium thiocyanate to 947.3 parts by weight
parts by weight of tetrachlorethylene. 12 under reflux
The mixture was strongly stirred at 2° C. for 1 hour to sufficiently dissolve the isotactic polypropylene. Lower the solution temperature to 105 °C,
4.2 parts by weight of t-butyl-peroxybenzoate were added and 135.2 parts by weight of chlorine gas were introduced at a rate of 0.6 parts by weight/min. After introducing a predetermined amount of chlorine gas, a ripening reaction was performed at the same temperature for 5 minutes, and the mixture was cooled to room temperature. Gas chromatographic analysis of the obtained tetrachloroethylene solution of chlorinated polypropylene (chlorine content: 36.7% by weight) revealed that the amount of hexachloroethane produced was 0.0 part by weight.
【0017】[0017]
【実施例2】 0.05重量部のチオシアン酸アンモ
ニウムを0.08重量部の1,3−ジメチル−2−イミ
ダゾリジノンに代えて実施例1と全く同様に塩素化を行
った。得られた塩素化ポリプロピレン(塩素含有量36
.3重量%)のテトラクロルエチレン溶液について、ガ
スクロマトグラフ分析を行った結果、ヘキサクロルエタ
ンの生成量は0.0 重量部であった。Example 2 Chlorination was carried out in exactly the same manner as in Example 1 except that 0.05 parts by weight of ammonium thiocyanate was replaced with 0.08 parts by weight of 1,3-dimethyl-2-imidazolidinone. The obtained chlorinated polypropylene (chlorine content 36
.. As a result of gas chromatographic analysis of a 3% by weight tetrachlorethylene solution, the amount of hexachloroethane produced was 0.0 part by weight.
【0018】[0018]
【実施例3】 0.05重量部のチオシアン酸アンモ
ニウムの添加量を0.08重量部のモノエタノ−ルアミ
ンに代えて実施例1と全く同様に塩素化を行った。得ら
れた塩素化ポリプロピレン(塩素含有量36.7重量%
)のテトラクロルエチレン溶液についてガスクロマトグ
ラフ分析を実施したところ、ヘキサクロルエタンの生成
量は0.0 重量部であった。Example 3 Chlorination was carried out in the same manner as in Example 1 except that 0.05 parts by weight of ammonium thiocyanate was replaced with 0.08 parts by weight of monoethanolamine. The obtained chlorinated polypropylene (chlorine content 36.7% by weight)
) was subjected to gas chromatography analysis, and the amount of hexachloroethane produced was 0.0 parts by weight.
【0019】[0019]
【比較例1】 チオシアン酸アンモニウムを添加しな
かった以外は実施例1と全く同様に塩素化を行った。得
られた塩素化ポリプロピレン(塩素含有量35.9重量
%)のテトラクロルエチレン溶液について、ガスクロマ
トグラフ分析を行った結果、ヘキサクロルエタンの生成
量は2.6 重量部であった。[Comparative Example 1] Chlorination was carried out in exactly the same manner as in Example 1 except that ammonium thiocyanate was not added. Gas chromatographic analysis of the obtained tetrachlorethylene solution of chlorinated polypropylene (chlorine content: 35.9% by weight) revealed that the amount of hexachloroethane produced was 2.6 parts by weight.
【0020】[0020]
【実施例4】 105.3 重量部のアイソタクチッ
クポリプロピレン(数平均分子量15000)及び0.
08重量部のモノエタノ−ルアミンを947.5 重量
部のテトラクロルエチレンに添加した。還流下122
℃、1時間強撹拌し、充分にアイソタクチックポリプロ
ピレンを溶解した。溶液温度を115 ℃に下げ、1.
1 重量部のジクミルパ−オキサイドを添加し、0.3
重量部/分の速度で135.2 重量部の塩素ガスを
導入した。所定の塩素ガスを導入した後、5分間、同温
度で熟成反応を行い室温まで冷却した。得られた塩素化
ポリプロピレン(塩素含有量37.0重量%)のテトラ
クロルエチレン溶液について、ガスクロマトグラフ分析
を行った結果ヘキサクロルエタンの生成量は0.0 重
量部であった。Example 4 105.3 parts by weight of isotactic polypropylene (number average molecular weight 15,000) and 0.3 parts by weight of isotactic polypropylene (number average molecular weight 15,000).
0.8 parts by weight of monoethanolamine were added to 947.5 parts by weight of tetrachlorethylene. Under reflux 122
The mixture was strongly stirred at ℃ for 1 hour to sufficiently dissolve the isotactic polypropylene. Lower the solution temperature to 115°C, 1.
Add 1 part by weight of dicumyl peroxide, and add 0.3 parts by weight of dicumyl peroxide.
135.2 parts by weight of chlorine gas were introduced at a rate of parts by weight/min. After introducing a predetermined amount of chlorine gas, a ripening reaction was carried out at the same temperature for 5 minutes, and the mixture was cooled to room temperature. Gas chromatographic analysis of the resulting tetrachlorethylene solution of chlorinated polypropylene (chlorine content: 37.0% by weight) revealed that the amount of hexachloroethane produced was 0.0 part by weight.
【0021】[0021]
【比較例2】 モノエタノ−ルアミンを添加しなかっ
た以外は実施例4と全く同様に塩素化を行った。得られ
た塩素化ポリプロピレン(塩素含有量36.6重量%)
のテトラクロルエチレン溶液についてガスクロマトグラ
フ分析を行った結果、ヘキサクロルエタンの生成量は5
.4 重量部であった。Comparative Example 2 Chlorination was carried out in the same manner as in Example 4 except that monoethanolamine was not added. Obtained chlorinated polypropylene (chlorine content 36.6% by weight)
As a result of gas chromatographic analysis of the tetrachlorethylene solution, the amount of hexachloroethane produced was 5.
.. It was 4 parts by weight.
【0022】上記から明らかなようにテトラクロルエチ
レンが塩素化されることによって生成するヘキサクロル
エタンの生成量に関して実施例1及び実施例2と比較例
1とを比較するとチオシアン酸アンモニウム、1,3
−ジメチル−2−イミダゾリジノンの添加効果が明らか
にあり、実施例3と比較例1の比較及び実施例4と比較
例2の比較からモノエタノ−ルアミンの添加効果は明ら
かにあり、何れの化合物もテトラクロルエチレンに対す
る塩素化を明らかに防止している。As is clear from the above, when comparing Examples 1 and 2 with Comparative Example 1 regarding the amount of hexachloroethane produced by chlorinating tetrachlorethylene, ammonium thiocyanate, 1,3
-Dimethyl-2-imidazolidinone clearly has an effect of addition, and from the comparison of Example 3 and Comparative Example 1 and the comparison of Example 4 and Comparative Example 2, it is clear that monoethanolamine has an effect of addition. It also clearly prevents chlorination of tetrachlorethylene.
【0023】[0023]
【発明の効果】本発明の効果を纏めると下記の通りであ
る。[Effects of the Invention] The effects of the present invention can be summarized as follows.
【0024】従来テトラクロルエチレンを溶剤としてポ
リオレフィンの塩素化を行った場合、ポリオレフィンの
塩素化と共にテトラクロルエチレンの塩素化が起こり、
主にヘキサクロルエタンが生成する。本発明はアルキル
アミン類、アルカノ−ルアミン類、含窒素複素環式アミ
ン類、チオシアン酸塩類、環式ウレア或は環式チオウレ
アの一種又は二種以上を含有させることにより、テトラ
クロルエチレンに対する塩素化を防止し、ポリオレフィ
ンのみを均一に塩素化することができる。Conventionally, when polyolefin was chlorinated using tetrachlorethylene as a solvent, chlorination of tetrachlorethylene occurred along with chlorination of polyolefin.
Mainly hexachloroethane is produced. The present invention is capable of chlorinating tetrachlorethylene by containing one or more of alkylamines, alkanolamines, nitrogen-containing heterocyclic amines, thiocyanates, cyclic ureas, or cyclic thioureas. It is possible to uniformly chlorinate only the polyolefin.
【0025】本発明はテトラクロルエチレンの塩素化物
であるヘキサクロルエタン等の生成がほとんどなく、従
来と異なり、回収したテトラクロルエチレンを蒸留せず
に再使用することができ、またヘキサクロルエタン等を
除去する工程が不要であり、工業的に実用性のある簡便
な塩素化ポリオレフィンの製造法である。The present invention hardly generates hexachloroethane, which is a chlorinated product of tetrachlorethylene, and unlike conventional methods, the recovered tetrachlorethylene can be reused without distillation, and hexachloroethane This is a simple and industrially practical method for producing chlorinated polyolefins, as there is no need for a step to remove .
【0026】本発明で得られた塩素化ポリオレフィンは
溶剤に対する均一溶解性から産業上の利用分野として特
にポリオレフィン系素材の塗装におけるプライマ−、塗
料のビヒクル、コ−ティング剤、接着剤、印刷インキの
バインダ−等に使用される。Due to its uniform solubility in solvents, the chlorinated polyolefin obtained in the present invention can be used as a primer in coating polyolefin materials, as a paint vehicle, as a coating agent, as an adhesive, and as a printing ink. Used for binders, etc.
Claims (3)
ン類又は含窒素複素環式アミン類の一種又は複数種の存
在下、ポリオレフィンをテトラクロルエチレンに溶解温
度以上で溶解し、ついでラジカル触媒下、光照射下又は
ラジカル触媒と光照射との併用の下において、塩素を導
入することによって、テトラクロルエチレンの塩素化を
抑制し、ポリオレフィンのみを塩素化することを特徴と
する塩素化ポリオレフィンの製造法。Claim 1: A polyolefin is dissolved in tetrachlorethylene at a temperature higher than its dissolution temperature in the presence of one or more of alkylamines, alkanolamines, or nitrogen-containing heterocyclic amines, and then irradiated with light under a radical catalyst. A method for producing a chlorinated polyolefin, which comprises suppressing the chlorination of tetrachlorethylene and chlorinating only the polyolefin by introducing chlorine under the conditions or under the combined use of a radical catalyst and light irradiation.
ン類又は含窒素複素環式アミン類の代わりにチオシアン
酸塩を使用する請求項1記載の塩素化ポリオレフィンの
製造法。2. The method for producing a chlorinated polyolefin according to claim 1, wherein a thiocyanate is used in place of the alkylamines, alkanolamines or nitrogen-containing heterocyclic amines.
ン類又は含窒素複素環式アミン類の代わりに一般式【化
1】 で表される環式ウレア、環式チオウレアを使用する請求
項1記載の塩素化ポリオレフィンの製造法。なお、一般
式 【化1】においてR1 及びR2 は低級アルキル基、
Xは酸素又は硫黄原子、nは2乃至3の整数を示す。 【化1】3. The chlorine according to claim 1, wherein a cyclic urea or a cyclic thiourea represented by the general formula [Chemical formula 1] is used instead of the alkylamines, alkanolamines or nitrogen-containing heterocyclic amines. Method for producing chemically modified polyolefins. In addition, in the general formula [Formula 1], R1 and R2 are lower alkyl groups,
X represents an oxygen or sulfur atom, and n represents an integer of 2 to 3. [Chemical formula 1]
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11398391A JPH04331208A (en) | 1991-04-17 | 1991-04-17 | Production of chlorinated polyolefin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11398391A JPH04331208A (en) | 1991-04-17 | 1991-04-17 | Production of chlorinated polyolefin |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04331208A true JPH04331208A (en) | 1992-11-19 |
Family
ID=14626121
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11398391A Pending JPH04331208A (en) | 1991-04-17 | 1991-04-17 | Production of chlorinated polyolefin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04331208A (en) |
-
1991
- 1991-04-17 JP JP11398391A patent/JPH04331208A/en active Pending
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