JPH04185617A - Chlorinated vinyl chloride resin excellent in solubility - Google Patents
Chlorinated vinyl chloride resin excellent in solubilityInfo
- Publication number
- JPH04185617A JPH04185617A JP31984390A JP31984390A JPH04185617A JP H04185617 A JPH04185617 A JP H04185617A JP 31984390 A JP31984390 A JP 31984390A JP 31984390 A JP31984390 A JP 31984390A JP H04185617 A JPH04185617 A JP H04185617A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- chlorinated
- viscosity
- polymerization
- 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 class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229920005989 resin Polymers 0.000 title claims abstract description 33
- 239000011347 resin Substances 0.000 title claims abstract description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000460 chlorine Substances 0.000 abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- 238000005660 chlorination reaction Methods 0.000 abstract description 6
- 230000001678 irradiating effect Effects 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 13
- -1 ethylene, propylene Chemical group 0.000 description 10
- 239000004801 Chlorinated PVC Substances 0.000 description 9
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 7
- 239000004800 polyvinyl chloride Substances 0.000 description 7
- 229920000915 polyvinyl chloride Polymers 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012736 aqueous medium Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 4
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000004711 α-olefin Substances 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
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 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
- 238000005342 ion exchange Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940083542 sodium Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000009849 vacuum degassing 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)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は有Ｉｌ溶荊に対する溶解性に優れ、低粘度で透
明な溶液となる塩素化塩化ビニル樹脂に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a chlorinated vinyl chloride resin that has excellent solubility in Il-containing solution and forms a low viscosity and transparent solution.
塩化ビニル系樹脂は、耐水性、耐候性、耐摩耗性、耐薬
品性等の性質に優れた樹脂であり、例えば金属等の表面
を塗布した場合、被塗布物の腐食、摩耗等を防止する優
れた効果を有する。Vinyl chloride resin is a resin with excellent properties such as water resistance, weather resistance, abrasion resistance, and chemical resistance. For example, when applied to metal surfaces, it prevents corrosion and abrasion of the object being coated. Has excellent effects.
塗布方法の中で最も一般的なものとして、樹脂を有機溶
剤に溶解して溶液とし、これを金属等の表面に塗布した
後、有機溶剤を揮発させる方法がある。この場合、塗布
溶液中の樹脂の濃度が高い長波塗布物表面に厚塗りが可
能で、また使用する溶剤の量も少なくて済みコスト面で
も有利である。Among the most common coating methods, there is a method in which a resin is dissolved in an organic solvent to form a solution, the solution is coated on the surface of a metal, etc., and then the organic solvent is evaporated. In this case, thick coating can be applied to the surface of the long-wave coated object where the concentration of resin in the coating solution is high, and the amount of solvent used is also small, which is advantageous in terms of cost.
また、塗布溶液は低粘度である程塗布作業が容易である
。しかるに、塩化ビニル系樹脂は有ｌ！溶剤に熔解した
場合、低濃度とした場合であっても高粘度の溶液となる
傾向があり、塗布溶液に通しているとは言い難い。Furthermore, the lower the viscosity of the coating solution, the easier the coating operation. However, vinyl chloride resin is available! When dissolved in a solvent, it tends to become a highly viscous solution even when the concentration is low, and it is difficult to say that it passes through the coating solution.
一方、塩化ビニル系樹脂のうちで塩化ビニルをこれと共
重合可能な他の単量体と共重合させて得られる共重合体
は、塩化ビニルの単独重合体よりも低粘度の溶液となる
ことが知られている。On the other hand, among vinyl chloride-based resins, copolymers obtained by copolymerizing vinyl chloride with other monomers that can be copolymerized with vinyl chloride result in solutions with lower viscosity than vinyl chloride homopolymers. It has been known.
また、塩化ビニル系樹脂を塩素化して得られる塩素化塩
化ビニル系樹脂は前記した塩化ビニル系樹脂の良好な特
性を持つと共に熱変形温度が塩化ビニル系樹脂より２０
〜４０°Ｃも高く、有機溶剤に溶解した場合に塩化ビニ
ル系樹脂よりも低粘度の溶液となるため、塩化ビニル系
樹脂より広い用途が開拓されつつある。In addition, the chlorinated vinyl chloride resin obtained by chlorinating the vinyl chloride resin has the good properties of the vinyl chloride resin described above, and has a heat distortion temperature of 20°C higher than that of the vinyl chloride resin.
It has a high temperature of ~40°C, and when dissolved in an organic solvent, it becomes a solution with a lower viscosity than vinyl chloride resin, so it is being developed for a wider range of uses than vinyl chloride resin.
しかし、塩化ビニル系樹脂のうちの共重合体や塩素化塩
化ビニル系樹脂は、塩化ビニル系樹脂のうちの塩化ビニ
ルの単独重合体に比べ低粘度の溶液を与えるとはいうも
のの、未だ満足し得る、塗布に適した低粘度溶液を提供
するまでには至っていない。However, although copolymers of vinyl chloride resins and chlorinated vinyl chloride resins provide solutions with lower viscosity than vinyl chloride homopolymers of vinyl chloride resins, they are still unsatisfactory. However, it has not yet been possible to provide a low viscosity solution suitable for application.
また、塩素化塩化ビニル系樹脂は有Ｉｍ溶剤に熔解した
場合、溶液は濁ったものとなり、更に塩素化塩化ビニル
系樹脂を熔解する有ｌ！溶剤の種類は多くない。従って
、塩素化塩化ビニル系樹脂は透明性が要求され、且つ多
種類の有１７８剤に熔解することが望まれる塗料等の塗
布用途には不適当である。In addition, when chlorinated vinyl chloride resin is dissolved in a solvent, the solution becomes cloudy and the chlorinated vinyl chloride resin is further dissolved. There are not many types of solvents. Therefore, chlorinated vinyl chloride resins are not suitable for coating applications such as paints, which require transparency and are desired to be soluble in a wide variety of 178 agents.
塩素化塩化ビニル系樹脂の上記問題点を改良するために
、下記の如き方法がｖＥ案されている；（１）セルロー
ス系分散剤のみを用いて、塩化ビニルとα−オレフィン
（エチレン、プロピレン）を油溶性重合開始剤の存在下
で共重合させ、α−オレフィンが２〜１０！量％含まれ
ている塩化ビニルの共重合体を得、次いで該共重合体を
塩素化することを特徴とする、低粘度で透明な溶液を生
成する塩素化塩化ビニル系樹脂の製造方法（特開昭６２
−８４．１０３） 。In order to improve the above-mentioned problems of chlorinated vinyl chloride resin, the following method has been proposed: (1) Using only a cellulose dispersant, vinyl chloride and α-olefin (ethylene, propylene) is copolymerized in the presence of an oil-soluble polymerization initiator to obtain 2 to 10 α-olefins! A method for producing a chlorinated vinyl chloride resin that produces a low-viscosity, transparent solution, characterized by obtaining a copolymer of vinyl chloride containing % of vinyl chloride, and then chlorinating the copolymer. 1986
-84.103).
（２）セルロース系分散剤のみを用いて、塩化ビニルと
α−オレフィン（エチレン、プロピレン）を油溶性重合
開始剤と油溶性連鎖移動剤との存在下で共重合させ、α
−オレフィンが２〜１０重量％含まれている塩化ビニル
の共重合体を得、次いで該共重合体を塩素化することを
特徴とする、低粘度で透明な溶液を生成する塩素化塩化
ビニル系樹脂の製造方法（特開昭６２−２５７９１４）
。(2) Using only a cellulose-based dispersant, vinyl chloride and α-olefin (ethylene, propylene) are copolymerized in the presence of an oil-soluble polymerization initiator and an oil-soluble chain transfer agent.
- a chlorinated vinyl chloride system producing a low-viscosity, transparent solution, characterized in that a copolymer of vinyl chloride containing 2 to 10% by weight of olefins is obtained and then the copolymer is chlorinated; Method for producing resin (Japanese Patent Application Laid-Open No. 62-257914)
.
（３）エチレン又はプロピレンが２〜２５重量％含まれ
ている塩化ビニルの共重合体を得、次いで該共重合体を
塩素化することを特徴とする、低粘度で透明な溶液を生
成する塩素化塩化ビニル系樹脂の製造方法（特開昭６３
−１０８００４）。(3) obtaining a copolymer of vinyl chloride containing 2 to 25% by weight of ethylene or propylene, and then chlorinating the copolymer to produce a low-viscosity, transparent solution of chlorine; Method for producing vinyl chloride resin (Unexamined Japanese Patent Publication No. 1983
-108004).
しかし乍ら、これらの方法により得られた塩素化塩化ビ
ニル系樹脂は比較的低粘度で透明な溶液を生成するもの
の溶液中の樹脂濃度も１５重量％程度と低く、従って改
良効果は充分とは言い難い。However, although the chlorinated vinyl chloride resins obtained by these methods produce transparent solutions with relatively low viscosity, the resin concentration in the solution is as low as about 15% by weight, so the improvement effect is not sufficient. It's hard to say.
本発明はかかる実情に鑑み、塩化ビニル単独重合体（以
下、ＰＶＣと記す）から得られる、多種類の有機溶剤に
高濃度で溶解するとともに、低粘度で透明な溶液を生成
し得る塩素化塩化ビニル樹脂（以下、ｃｐｖｃと記す）
を提供することを目的とする。In view of these circumstances, the present invention has developed a chlorinated chloride which is obtained from vinyl chloride homopolymer (hereinafter referred to as PVC) and is soluble in a wide variety of organic solvents at high concentration and can produce a low viscosity and transparent solution. Vinyl resin (hereinafter referred to as CPVC)
The purpose is to provide
即ち、本発明は平均重合度が３００以下のＰＶＣを塩素
化して得られる有機溶剤に対する溶解性に優れ、低粘度
で透明な溶液となるｃｐｖｃを内容とするものである。That is, the present invention involves a CPVC obtained by chlorinating PVC with an average degree of polymerization of 300 or less, which has excellent solubility in organic solvents and forms a low-viscosity, transparent solution.
ＰＶＣの重合は、！！！濁重合法によって行われる。Polymerization of PVC is! ! ! It is carried out by the turbidity polymerization method.
即ち、重合器内に水と分散剤と重合開始剤を仕込み、脱
気した後塩化ビニルを圧入して懸濁重合する。That is, water, a dispersant, and a polymerization initiator are charged into a polymerization vessel, and after deaeration, vinyl chloride is forced into the vessel and suspension polymerization is carried out.
分散剤としては、合成又は天然高分子系分散剤、非イオ
ン界面活性剤、アニオン界面活性剤等が挙げられる０合
成又は天然高分子系分散剤としては、メチルセルロース
、エチルセルロース、ヒドロキシメチルセルロース、ヒ
ドロキシプロピルメチルセルロース等のセルロース誘導
体や、部分鹸化ポリ酢酸ビニル、ポリビニルアルコール
、ポリビニルピロリドン、ポリエチレンオキサイド′等
の水溶性有機高分子化合物等が挙げられる。非イオン界
面活性剤としては、ポリオキシエチレンラウリルエーテ
ル、ポリオキシエチレンセチルエーテル、ポリオキシエ
チレンステアリルエーテル、ポリオキシエチレンオクチ
ルフェノールエーテル等のポリオキンエチレンアルキル
エーテルや、オキシエチレン・オキシプロピレンブロッ
クポリマー等が挙げられる。アニオン界面活性剤として
は、ラウリル硫酸ナトリウム１ ドデシルベンゼンスル
ボン酸ナトリウム、ポリオキシュチレンアルキルエーテ
ル硫酸ナトリウム、ポリオキシエチレンアルキルフェニ
ルエーテルｔｆＪＢナトリウム等が挙げられる。上記分
散剤は単独又は２種以上組み合わせて用いられる１分散
剤の使用量は塩化ビニル１００重量部番こ対し０．０】
〜１．０重量部の範囲が好ましい。Examples of dispersants include synthetic or natural polymeric dispersants, nonionic surfactants, anionic surfactants, etc. 0 Examples of synthetic or natural polymeric dispersants include methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxypropylmethylcellulose and water-soluble organic polymer compounds such as partially saponified polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidone, and polyethylene oxide. Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene octylphenol ether, and oxyethylene/oxypropylene block polymers. It will be done. Examples of the anionic surfactant include sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium polyoxytylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether tfJB, and the like. The above dispersants may be used alone or in combination of two or more.The amount of dispersant used is 0.0 per 100 parts by weight of vinyl chloride.]
A range of 1.0 parts by weight is preferred.
重合開始剤としては、ペンゾイルバーオキサイド、ラウ
ロイルパーオキサイド、３，５．５−トリメチルヘキサ
ノイルパーオキサイド、ジイソブロビルパーオキシジカ
ーボ７一ト、ジー２−エチルヘキシルパーオキシジカー
ボネート、ジェトキシエチルパーオキシジカーボ７一ト
、ジー３−メトキシブチルパーオキシジカーボネート、
ｔｅｒｔ。As a polymerization initiator, penzoyl peroxide, lauroyl peroxide, 3,5.5-trimethylhexanoyl peroxide, diisobrobyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, jetoxyethylperoxy dicarbonate, di-3-methoxybutyl peroxydicarbonate,
tert.
−ブチルパーオキシふオデカネート等の有機過酸化物、
２．２′−アゾビス（２，４−ジメチルバレロニトリル
）、アゾビスイソブチロニトリル等のアブ化合物等が挙
げられ、これらは単独又は２種以上組み合わせて用いら
れる。重合開始剤の使用量は塩化ビニル１００重量部に
対し０．００１〜２重量部が好ましい。- organic peroxides such as butyl peroxyfluorodecanate,
Ab compounds such as 2.2'-azobis(2,4-dimethylvaleronitrile) and azobisisobutyronitrile may be mentioned, and these may be used alone or in combination of two or more. The amount of the polymerization initiator used is preferably 0.001 to 2 parts by weight per 100 parts by weight of vinyl chloride.
水性媒体は塩化ビニル１００重量部に対し５０〜３００
重量部使用するのが好ましく、また重合温度は５０〜９
０°Ｃが好ましい。The aqueous medium is 50 to 300 parts by weight of vinyl chloride.
It is preferable to use parts by weight, and the polymerization temperature is 50 to 9.
0°C is preferred.
また、本発明では重合の際に連鎖移動剤を使用してもよ
い。、連鎖移動剤としては、ジクロロエタン、トリクロ
ロエタン、四塩化炭素等の塩素化合物、２−メルカプト
エタノール、オクチルメルカプタン、ドデシルメルカプ
タン等のメルカプト化合物等が挙げられ、これらは単独
又は２１１以上組み合わせて用いられる。使用量は塩化
ビニル１００重量部に対して０．０１〜５Ｍ量部が好ま
しい。Furthermore, in the present invention, a chain transfer agent may be used during polymerization. Examples of the chain transfer agent include chlorine compounds such as dichloroethane, trichloroethane, and carbon tetrachloride, and mercapto compounds such as 2-mercaptoethanol, octylmercaptan, and dodecylmercaptan, and these may be used alone or in combination of 211 or more. The amount used is preferably 0.01 to 5M parts per 100 parts by weight of vinyl chloride.
更に、重合の際に抗酸化剤、例えばジステアリルチオジ
ブ口ビオ７−ト、ジラウリルチオジプロピオネート等の
含硫黄化合物、ｔｅｒｔ、−ブチルヒどロキシアニソー
ル、ジーｔｅｒｔ、−ブチルヒドロキシトルエン等のフ
ェノール系化合物等を単独又は２種以上組み合わせて添
加してもよい。Furthermore, during the polymerization, antioxidants such as sulfur-containing compounds such as distearylthiodibutyl 7-ate and dilaurylthiodipropionate, tert, -butylhydroxyanisole, di-tert, -butylhydroxytoluene, etc. are added. Phenol compounds and the like may be added alone or in combination of two or more.
以上の如くして、平均重合度が３００以下のＰＶＣが得
られる。In the manner described above, PVC having an average degree of polymerization of 300 or less can be obtained.
得られたＰＶＣは水性媒体から分離され又は分離されず
そのまま塩素化される。The PVC obtained can be separated from the aqueous medium or chlorinated without being separated.
塩素化の方法は特に限定されず公知の方法が使用される
。例えば、前記のようにして得られた水性媒体中のＰＶ
Ｃをそのまま光塩素化してもよく、また共重合体と水性
媒体を分離した後、再度該Ｐ■Ｃを水性媒体中に懸濁さ
せて塩素化を行ってもよい。The method of chlorination is not particularly limited, and known methods can be used. For example, PV in the aqueous medium obtained as described above
C may be photochlorinated as it is, or after separating the copolymer from the aqueous medium, the P2C may be suspended again in the aqueous medium and chlorinated.
塩素化は、紫外線照射装置を設けた塩素化反応装置内に
Ｉｐｖｃと水性媒体を仕込み、次いで塩素を導入し紫外
線を照射することによって行われる。Chlorination is carried out by charging IPVC and an aqueous medium into a chlorination reaction apparatus equipped with an ultraviolet irradiation device, then introducing chlorine and irradiating it with ultraviolet rays.
上記の如くして得られるＣＰＶＣの塩素含有量は、特に
臨界的な意味はないが６０〜７０重量％が好ましい。Although the chlorine content of the CPVC obtained as described above is not particularly critical, it is preferably 60 to 70% by weight.
本発明のｃｐｖｃは種々の有ｍ溶刑に高濃度に溶解し、
得られた溶液は高ａ炭にＣＰＶＣが溶解しているにもか
かわらず低粘度でかつ透明である。The CPVC of the present invention dissolves at high concentration in various methanol solutions,
The resulting solution has a low viscosity and is transparent despite the fact that CPVC is dissolved in the high a carbon.
かくして、塗料、インキベース、接着剤等に有用である
。Thus, it is useful in paints, ink bases, adhesives, etc.
有機溶剤としては、メチルエチルケトン、メチルイソブ
チルケトン、シクロヘキサノン等のケトン系溶剤、トル
エン、キンレン等の芳香族系溶剤、テトラヒドロフラン
、ジメチルホルムアミド、ジメチルホルホキンド等の非
プロトン系溶剤、酢酸メチル、酢酸エチル、酢酸ブチル
、酢酸アミル等のエステル系溶剤、四塩化炭素、クロロ
ホルム、塩化メチレン等の塩素系溶剤等の単独又は２種
以上の混合物が挙げられる。Examples of organic solvents include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic solvents such as toluene and quinolene, aprotic solvents such as tetrahydrofuran, dimethylformamide, and dimethylforhoquinde, methyl acetate, ethyl acetate, Examples include ester solvents such as butyl acetate and amyl acetate, and chlorine solvents such as carbon tetrachloride, chloroform and methylene chloride, either singly or in a mixture of two or more.
以下に実施例及び比較例を挙げて本発明を更に詳細に説
明するが、これらは何ら本発明を限定するものではない
。The present invention will be explained in more detail with reference to Examples and Comparative Examples below, but these are not intended to limit the present invention in any way.
実施例１〜９、比較例１〜４
攪拌翼を備えた内容積１５ｆの重合器に、イオン交換水
２５０重量部、ｔｅｒｍ、−ブチルバーオキシヱオデカ
：＃−）０．１５重量部、３．５．５−トリメチルヘキ
サノイルバーオキサイＩ’０．１５ＭＷｔ部、第１表に
示した量の２−メルカプトエタノール及び分散剤を仕込
み、重合器内を真空脱気した後塩化ビニル１００重量部
を圧入して、重合温度６８°Ｃで７時間重合した。重合
後のスラリーを脱水してＰｖＣを得た。第１表に、この
ＰＶＣの平均重合度を示した。Examples 1 to 9, Comparative Examples 1 to 4 In a polymerization vessel with an internal volume of 15 f equipped with a stirring blade, 250 parts by weight of ion-exchanged water, 0.15 parts by weight of term, -butylbaroxyeodeca: #-), 3.5.5-Trimethylhexanoyl peroxide I'0.15 MWt part, 2-mercaptoethanol and dispersant in the amounts shown in Table 1 were charged, and after vacuum degassing the inside of the polymerization vessel, 100 weight of vinyl chloride was added. A portion was press-fitted and polymerized at a polymerization temperature of 68°C for 7 hours. The slurry after polymerization was dehydrated to obtain PvC. Table 1 shows the average degree of polymerization of this PVC.
二〇ＰＶＣ１ｋｇＣ乾燥品換算）とイオン交換水３ｋｇ
を内容積８ｆのガラス製反応器に仕込んだ。20 PVC 1kg (dry product equivalent) and ion exchange water 3kg
was charged into a glass reactor having an internal volume of 8 f.
反応器内の空気を窒素で置換した後、５０ ’Ｃで反応
器に塩素ガスを連続的に導入し、反応器外部がら水銀灯
〔■東芝製５ＨＬ−１００Ｕシ２〕を点灯して光塩素化
を行った。塩素含有量が所定の値に達した時に塩素化反
応を停止し、反応器内の塩素ガスを窒素で置換後スラリ
ーを取り出し、脱水、乾燥してｃｐｖｃを得た。After replacing the air in the reactor with nitrogen, chlorine gas was continuously introduced into the reactor at 50'C, and a mercury lamp [■ Toshiba 5HL-100U Shi2] was turned on from outside the reactor for photochlorination. I did it. When the chlorine content reached a predetermined value, the chlorination reaction was stopped, and after replacing the chlorine gas in the reactor with nitrogen, the slurry was taken out, dehydrated, and dried to obtain CPVC.
このｃｐｖｃをメチルエチルケトンに溶解し２０重量％
濃度とした溶液の透明性を肉眼で評価し、また２０°Ｃ
における粘度を測定した。その結果を第１表に示した。Dissolve this CPVC in methyl ethyl ketone and make 20% by weight.
Visually evaluate the transparency of the solution at 20°C.
The viscosity was measured. The results are shown in Table 1.
粘度の測定にはＢ型粘度計Ｃ１１！京計器製〕を使用し
た。B-type viscometer C11 for measuring viscosity! [manufactured by Kyo Keiki] was used.
また、このＣＰＶＣをメチルエチルケトン、酢酸エチル
又はトルエンにそれぞれ溶解し３０重量％濃度とした溶
液の透明性についても同様に評価した。結果を第１表に
示した。Furthermore, the transparency of solutions obtained by dissolving this CPVC in methyl ethyl ketone, ethyl acetate, or toluene to give a concentration of 30% by weight was similarly evaluated. The results are shown in Table 1.
＊１ＭＥＫ：メチルエチルケトン
ネ２透明性：下記の基準により３段階評価を行った；Ｏ
：透明
×：白濁（不溶分が少ない）
××：白濁（不溶分が多い）
＊３使用量（重量部）：
塩化ビニル１００重量部に対する部数
牢４２ＭＥ：２−メルカプトエタノール＊５ＭＣ：ヒド
ロキシプロピルメチルセルロース〔信越化学工業−製肛
９０ ＳＨ１００）＊６ＰＥＯ＋ポリエチレンオキサイ
ド
〔住友精化■製ＰＥ０−１５）
上記第１表の結果から、実施例１〜９は比較例１〜４に
比べて、溶液の粘度が低くまた溶液の透明性が良好であ
り、各種溶剤に対する溶解性が良好であることがわかる
。*1 MEK: Methyl ethyl ketone 2 Transparency: Three-stage evaluation was performed based on the following criteria: O
:Transparent [Shin-Etsu Chemical Co., Ltd. - 90 SH100) *6 PEO + polyethylene oxide [PE0-15 manufactured by Sumitomo Seika Chemical Co., Ltd.] From the results in Table 1 above, Examples 1 to 9 have lower solution viscosity than Comparative Examples 1 to 4. It can be seen that the solution has a low value and good transparency, and has good solubility in various solvents.
〔作用・効果］
軟土の通り、重合度が３００以下のＰｖＣを塩素化して
得られるｃｐｖｃは、有機溶剤に対する溶解性に優れる
とともに、低粘度で透明なｆ４液となり、塗料、インキ
ベース、接着側等に好適で、その工業的価値は極めで高
い。[Action/Effect] As with soft soil, CPVC obtained by chlorinating PvC with a degree of polymerization of 300 or less has excellent solubility in organic solvents and becomes a low-viscosity, transparent F4 liquid, which can be used in paints, ink bases, and adhesives. It is suitable for side surfaces, etc., and its industrial value is extremely high.
Claims (1)
して得られる、有機溶剤に対する溶解性に優れ、低粘度
で透明な溶液となる塩素化塩化ビニル樹脂。1. A chlorinated vinyl chloride resin that is obtained by chlorinating a vinyl chloride resin with an average degree of polymerization of 300 or less, which has excellent solubility in organic solvents and forms a low-viscosity, transparent solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31984390A JPH04185617A (en) | 1990-11-21 | 1990-11-21 | Chlorinated vinyl chloride resin excellent in solubility |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31984390A JPH04185617A (en) | 1990-11-21 | 1990-11-21 | Chlorinated vinyl chloride resin excellent in solubility |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04185617A true JPH04185617A (en) | 1992-07-02 |
Family
ID=18114839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31984390A Pending JPH04185617A (en) | 1990-11-21 | 1990-11-21 | Chlorinated vinyl chloride resin excellent in solubility |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04185617A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6242539B1 (en) | 1997-07-29 | 2001-06-05 | Kaneka Corporation | Process for production of chlorinated polyvinyl chloride resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52148546A (en) * | 1976-06-04 | 1977-12-09 | Tokuyama Sekisui Ind Corp | Process for production of sintering body of chlorinated vinyl chloride resin |
| JPS61250047A (en) * | 1985-04-30 | 1986-11-07 | Tokuyama Sekisui Kogyo Kk | Chlorinated polyvinyl chloride resin composition |
| JPH02242840A (en) * | 1989-03-16 | 1990-09-27 | Tokuyama Sekisui Ind Corp | Chlorinated vinyl chloride-based resin composition |
-
1990
- 1990-11-21 JP JP31984390A patent/JPH04185617A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52148546A (en) * | 1976-06-04 | 1977-12-09 | Tokuyama Sekisui Ind Corp | Process for production of sintering body of chlorinated vinyl chloride resin |
| JPS61250047A (en) * | 1985-04-30 | 1986-11-07 | Tokuyama Sekisui Kogyo Kk | Chlorinated polyvinyl chloride resin composition |
| JPH02242840A (en) * | 1989-03-16 | 1990-09-27 | Tokuyama Sekisui Ind Corp | Chlorinated vinyl chloride-based resin composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6242539B1 (en) | 1997-07-29 | 2001-06-05 | Kaneka Corporation | Process for production of chlorinated polyvinyl chloride resin |
| US6384149B2 (en) | 1997-07-29 | 2002-05-07 | Kaneka Corporation | Process for production of chlorinated polyvinyl chloride resin |
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