JP5521213B2 - Chlorinated polyether copolymer and process for producing the same - Google Patents

Description

  The present invention relates to a novel chlorinated polyether copolymer having a high chlorine content, excellent thermal stability and storage stability, and a method for producing the same.

  The chlorinated polyether copolymer of the present invention can be expected to be applied to polyurethane-based paints, adhesives, primers, ink binders and the like that are excellent in flame retardancy of polyurethane and adhesion to plastic materials.

  The polyol compound is useful as a resin raw material such as polyurethane and polyester, a surfactant, and a lubricant. Many types of polyol compounds such as polyethers and polyesters are commercially available, and in combination with isocyanate compounds, they can be used in rigid, semi-rigid, or flexible foams, or polyurethane products such as elastomers, paints, and adhesives. Has been deployed.

  Generally, polyurethane is flammable, and it has been proposed to add various flame retardants to make it flame retardant (for example, see Non-Patent Document 1).

  However, a large amount of flame retardant is required to achieve the target flame retardant effect. In addition, since the flame retardant is a low-molecular compound, there is a problem that the flame retardant moves to the surface of the polyurethane with time and causes stickiness and the like.

  On the other hand, as a method for imparting flame retardancy to polyurethane, a method using a polyol containing halogen has been reported. Such halogen-containing polyol uses polyhydric alcohol or polyether polyol as a starting material, and contains chlorine such as epichlorohydrin or 4,4,4-trichloro-1,2-epoxybutane in the presence of an acid catalyst. It can be synthesized by a method of adding an alkylene oxide (for example, see Patent Documents 1 and 2) or a method of chlorinating a polyether polyol using chlorine gas in a solvent (for example, see Patent Document 3).

  Further, it is known that halogen-containing polyols are useful not only for flame retardancy modification of polyurethane but also as a raw material for polyurethane paints and ink binders that have improved adhesion to plastic materials (for example, Patent Document 3). 4).

  As mentioned above, halogen-containing polyols are useful as polyurethane raw materials, but their use is limited. This is because the halogen-containing polyol obtained from epichlorohydrin has a low chlorine content and a small effect of improving flame retardancy, and since it has only primary chlorine, the effect of improving the plastic adhesion is small. In addition, 4,4,4-trichloro-1,2-epoxybutane is difficult to obtain industrially because of its many synthesis steps and expensive, and the resulting polyol is easily decomposed, so care must be taken in handling. . Furthermore, a synthesis example of a polyol obtained from 1,4-dichloro-2,3-epoxybutane having an intermediate chlorine content between epichlorohydrin and 4,4,4-trichloro-1,2-epoxybutane was reported. However, (for example, refer to Patent Document 5), impurities insoluble in the solvent are by-produced.

  On the other hand, a polyol obtained by a method of chlorinating a polyether polyol has a problem of poor thermal stability and dehydrochlorination over time.

U.S. Pat. No. 4,282,332 JP 59-157120 A JP 59-196361 A JP-A-6-172737 US Pat. No. 3,251,852

“The latest polyurethane design / modification and advanced technology”, Technical Information Association, March 2007, p.305

  The present invention has been made in view of the above-mentioned background art, and its purpose is to provide a novel chlorinated polyether copolymer having a high chlorine content and excellent thermal stability, storage stability, handling properties, and solvent solubility. It is to provide a polymer.

  As a result of intensive studies to solve the above problems, the present inventors have found a chlorinated polyether copolymer having a specific structure, and have completed the present invention.

  That is, the present invention relates to the following chlorinated polyether copolymer and a method for producing the same.

  [1] The following formula (1)

で示される構造単位Ａと、下記式（２）

And a structural unit A represented by the following formula (2)

（上記式（２）中、Ｒ_１は水素原子、又はＣＨ_２Ｃｌ基を表す。）
で示される構造単位Ｂ及び／又は下記式（３）

(In the above formula (2), R ₁ represents a hydrogen atom or a CH ₂ Cl group.)
The structural unit B shown by and / or following formula (3)

［上記式（３）中、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５は各々独立して、水素原子、ハロゲン原子を含まない炭素数が１〜１０のアルキル基、又はハロゲン原子を含まない炭素数６〜１０のアリール基を表す。］
で示される構造単位Ｃとを含む塩素化エーテル共重合体であって、構造単位Ａを１〜９９モル％含有することを特徴とする塩素化エーテル共重合体。

[In the above formula (3), R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms not containing a halogen atom, or a carbon not containing a halogen atom. The aryl group of several 6-10 is represented. ]
A chlorinated ether copolymer containing 1 to 99 mol% of the structural unit A, which comprises a structural unit C represented by formula (1).

  [2] The chlorinated polyether copolymer as described in [1] above, which has a hydroxyl value of 1 to 1000 (mgKOH / g).

[3] The chlorinated polyether copolymer according to claim 1 or 2, wherein a viscosity at 25 ° C is 10 to 10 ⁷ mPa · s.

  [4] Using an active hydrogen-containing compound as a polymerization initiator and in the presence of an acid catalyst, 3,4-dichloro-1,2-epoxybutane, 1,4-dichloro-2,3-epoxybutane, epichlorohydride The chlorine according to any one of [1] to [3], wherein ring-opening copolymerization is carried out with phosphorus and one or more monomers selected from alkylene oxides having 2 to 20 carbon atoms. For producing a fluorinated polyether copolymer.

  [5] The method for producing a chlorinated polyether copolymer according to the above [4], wherein the active hydrogen-containing compound is a polyether polyol having a hydroxyl value of 120 to 1500 (mgKOH / g).

  The chlorinated polyether copolymer of the present invention has a high chlorine content and is excellent in thermal stability, storage stability, and handling properties. Further, the chlorinated polyether copolymer of the present invention can be expected as a raw material for polyurethane excellent in flame retardancy and adhesion to plastic materials.

  The present invention is described in detail below.

  The chlorinated polyether copolymer of the present invention comprises a structural unit A represented by the above formula (1), a structural unit B represented by the above formula (2) and / or a structural unit C represented by the above formula (3). A chlorinated ether copolymer containing 1 to 99 mol% of the structural unit A.

R ₁ in the above formula (2) represents a hydrogen atom or a CH ₂ Cl group.

In the above formula (3), R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which does not contain a halogen atom, or a halogen atom. An aryl group having 6 to 10 carbon atoms is represented.

Specific examples of R ₂ , R ₃ , R ₄ , and R ₅ include a hydrogen atom; a linear alkyl group such as a methyl group, an ethyl group, and a propyl group; a branched alkyl group such as an isopropyl group; and an alicyclic alkyl such as a cyclohexyl group. Groups, phenyl groups, substituted phenyl groups such as p-methylphenyl groups, and the like, but are not limited thereto.

  In the chlorinated polyether copolymer of the present invention, when the above structural unit A is less than 1 mol%, the chlorine content is small and it is difficult to obtain the intended modification effect and the solubility in the solvent may be reduced. When it exceeds 99 mol%, the viscosity becomes too high and the fluidity is lowered. Therefore, it is permissible that the structural unit represented by the above formula (1) is in the range of 1 to 99 mol%, preferably 5 to 90 mol%, particularly preferably 10 in the chlorinated polyether copolymer. It is in the range of ˜80 mol%.

  In the chlorinated polyether copolymer of the present invention, as the copolymer component, the above-mentioned structural unit B and / or the above-mentioned structural unit C can be arbitrarily selected. In order to obtain a copolymer having an easy viscosity range, the structural unit C is contained in the chlorinated polyether copolymer, preferably in the range of 5 to 90 mol%, more preferably in the range of 10 to 80 mol%. It is preferable.

  Note that the total number of moles of the structural units A to C contained in the chlorinated polyether copolymer does not exceed 100 mol%.

  In addition, the chlorinated polyether copolymer of the present invention is generally polymer-terminated, branched, and generally known polyether (sometimes referred to as polyether polyol or polyoxyalkylene polyol). It may have a hydroxyl group at the chain end or the like. The amount of hydroxyl groups in the chlorinated polyether copolymer of the present invention can be calculated as a hydroxyl value (mgKOH / g).

  The hydroxyl value of the chlorinated polyether copolymer of the present invention can be set according to the intended use and is not particularly limited. For example, the polyurethane raw material is usually 1 to 1000 (mgKOH / g). More preferably, the range of 10 to 800 (mg KOH / g) is preferable. The hydroxyl value can be calculated according to the method of JIS K1557.

The chlorinated polyether copolymer of the present invention is liquid to solid, but its state changes depending on the composition, the number of branches, and the molecular weight. In order to be used as a polyurethane raw material, it is preferable that it is liquid and exhibits fluidity at 20 to 100 ° C. for ease of handling. Among them, for use as a polyurethane foam, the viscosity at 25 ° C. is usually in the range of 10 to 10 ⁷ mPa · s, preferably 10 ² to 10 ⁶ mPa · s, and more preferably 10 ² to 10 ⁵ mPa · s. It is.

  The chlorine content in the chlorinated polyether copolymer of the present invention can be arbitrarily adjusted according to the purpose of use and is not particularly limited, but is usually 5 to 50% by weight, more preferably 10 to 46% by weight. % Range. By setting the chlorine content to 5% by weight or more, for example, the improvement effect of flame retardancy and plastic adhesion when made into polyurethane is improved, but it is difficult to synthesize a copolymer having a chlorine content exceeding 50% by weight. It is.

  Further, the chlorinated polyether copolymer of the present invention binds to a chlorine atom bonded to a primary carbon group (hereinafter referred to as “primary chlorine atom”) and a secondary carbon group as shown in the above formula (1). It is characterized by having a chlorine atom (hereinafter referred to as “secondary chlorine atom”). The proportion of secondary chlorine atoms in the total chlorine atoms contained in the chlorinated polyether copolymer can be arbitrarily adjusted according to the purpose of use and is not particularly limited, but is usually in the range of 5 to 50%. It is. By making the proportion of secondary chlorine atoms 5% or more, for example, the effect of improving the flame retardancy and plastic adhesion when polyurethane is used is improved, but the proportion of secondary chlorine atoms exceeds 50%. The synthesis of the polymer is difficult.

  The method for producing the chlorinated polyether copolymer of the present invention is not particularly limited. For example, 3,4-dichloro-1 is used in the presence of an acid catalyst using an active hydrogen-containing compound as a polymerization initiator. , 2-epoxybutane, 1,4-dichloro-2,3-epoxybutane, epichlorohydrin, and one or more monomers selected from the group consisting of alkylene oxides having 2 to 20 carbon atoms And a ring-opening copolymerization method.

  Here, the structural unit A is derived from 3,4-dichloro-1,2-epoxybutane, the structural unit B is derived from 1,4-dichloro-2,3-epoxybutane and epichlorohydrin, The structural unit C is derived from an alkylene oxide having 2 to 20 carbon atoms.

  Specific examples of the alkylene oxide having 2 to 20 carbon atoms include ethylene oxide, propylene oxide, butylene oxide, 2,3-butylene oxide, isobutylene oxide, butadiene monooxide, pentene oxide, styrene oxide, and cyclohexene oxide. A C2-C20 alkylene oxide may be used independently and may be used in mixture of 2 or more types.

  If the chlorinated polyether of the present invention can be produced, the ratio of the above-mentioned monomers can be arbitrarily set according to the intended use, but the obtained chlorinated polyether copolymer can be used as a fluid liquid. For handling, the proportion of 3,4-dichloro-1,2-epoxybutane is usually used in all monomers used in the reaction (including 3,4-dichloro-1,2-epoxybutane, the same applies hereinafter). The range is from 1 to 99 mol%, and the proportion of the alkylene oxide having 2 to 20 carbon atoms is preferably from 5 to 90 mol%, more preferably from 10 to 80 mol%.

  In addition, 3,4-dichloro-1,2-epoxybutane, 1,4-dichloro-2,3-epoxybutane, epichlorohydrin, and carbon number 2 contained in all monomers used for the reaction The total number of moles of ˜20 alkylene oxides does not exceed 100 mole%.

  Examples of the active hydrogen-containing compound used as the polymerization initiator include a hydroxy compound, an amine compound, a carboxylic acid compound, a phenol compound, phosphoric acid, and a thiol compound. Specifically, water, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, sorbitol, shoelace, etc. Examples include hydroxy compounds; amine compounds such as ethylenediamine; carboxylic acid compounds such as benzoic acid and adipic acid; phenol compounds such as bisphenol A; thiol compounds such as ethanedithiol and butanedithiol. These can be appropriately selected depending on the application.

  In addition, a polyether polyol having a hydroxyl group can be used as a polymerization initiator. In this case, a hydroxyl value of 120 to 1500 (mgKOH / mg) having excellent affinity with the monomer used and low viscosity. The polyether polyol of g) is preferred. A polymerization initiator may be used independently and may be used in mixture of several types.

  There is no restriction | limiting in particular as the usage-amount of a polymerization initiator, What is necessary is just to adjust arbitrarily the ratio of all the monomers and a polymerization initiator according to the molecular weight of the target chlorinated polyether copolymer. Among them, in order to obtain a chlorinated polyether suitable as a raw material for polyurethane, the number of moles of active hydrogen contained in the polymerization initiator is 0.02 with respect to the total number of moles of all monomers used in the reaction. It is preferable to set the amount to be ˜2 times the molar amount.

  As the acid catalyst, a conventionally known acid catalyst can be used. For example, mineral acids such as sulfuric acid, phosphoric acid and hydrochloric acid; boron halide compounds such as boron trifluoride and boron trichloride; aluminum chloride; Aluminum halide compounds such as aluminum bromide; tin compounds such as tin tetrafluoride and tin tetrachloride; antimony compounds such as antimony fluoride and antimony chloride; iron compounds such as ferric chloride; phosphorus such as phosphorus pentafluoride Compounds; zinc halide compounds such as zinc chloride; titanium compounds such as titanium tetrachloride; zirconium compounds such as zirconium chloride; beryllium compounds such as beryllium chloride; triphenyl boron, tri (t-butyl) boron, tris (pentafluorophenyl) ) Boron, bis (pentafluorophenyl) -t-butyl boron, bis (pentafluorophenyl) boron fluoride, di ( -Butyl) boron fluoride, (pentafluorophenyl) organic boron compounds such as boron difluoride; triethylaluminum, triphenylaluminum, diphenyl-t-butylaluminum, tris (pentafluorophenyl) aluminum, bis (pentafluorophenyl) Organic aluminum compounds such as -t-butylaluminum, bis (pentafluorophenyl) aluminum fluoride, di (t-butyl) aluminum fluoride, (pentafluorophenyl) aluminum difluoride, (t-butyl) aluminum difluoride An organic zinc compound such as diethylzinc.

  In addition, a Lewis acid can be used as the acid catalyst. In that case, it may be used alone or as a complex with various organic compounds. Examples of the complex of Lewis acid and an organic compound include ether complexes such as dimethyl ether complex, diethyl ether complex, and THF (tetrahydrofuran) complex; carboxylic acid complexes such as acetic acid complex; alcohol complexes; amine complexes;

  Moreover, an acid catalyst may be used independently and may use 2 or more types together.

The amount of the acid catalyst to be used is not particularly limited, but since all chlorinated polyether copolymers can be produced efficiently, all the unit amounts including 3,4-dichloro-1,2-epoxybutane to be used. It is preferable to use in the range of 1 × 10 ^{−5 to} 0.1 mol relative to 1 mol of the body.

  Further, when the chlorinated polyether copolymer of the present invention is produced, it may be produced either in a solvent or without a solvent, and a highly viscous high molecular weight chlorinated polyether copolymer is produced. In this case, it is preferable to use a solvent. It is also possible to add a solvent after polymerization without solvent.

  Here, the solvent can be used without particular limitation as long as it does not adversely affect the polymerization. For example, hydrocarbons such as hexane and heptane; aromatic compounds such as toluene and xylene; chlorinated products such as methylene chloride, chloroform, dichloroethane, trichloroethane and dichlorobenzene; ethers such as ethyl ether; nitro compounds such as nitromethane and nitrobenzene A sulfide such as carbon disulfide; an alkylene glycol dialkyl ether such as propylene glycol dimethyl ether; You may use the above-mentioned solvent individually or in mixture of 2 or more types.

  Although there is no restriction | limiting in particular in the usage-amount of a solvent, 0.1 times-5 times with respect to the total weight of all the monomers and a polymerization initiator in consideration of the productivity and collection | recovery efficiency of a chlorinated polyether copolymer. Is preferred.

  The production conditions are selected from 3,4-dichloro-1,2-epoxybutane, 1,4-dichloro-2,3-epoxybutane, epichlorohydrin, and alkylene oxide having 1 to 10 carbon atoms. Any conditions may be used as long as at least one monomer is capable of ring-opening copolymerization. For example, the range of polymerization temperature -78-150 degreeC and the polymerization time 10 minutes-48 hours can be mentioned. In particular, since a chlorinated polyether excellent in hue is obtained, the polymerization temperature is preferably in the range of −50 to 120 ° C. and the polymerization time is in the range of 30 minutes to 24 hours.

  The chlorinated polyether copolymer of the present invention is useful for polyurethane raw materials, polyester raw materials, surfactant raw materials, and the like. Particularly, the chlorinated polyether copolymer having a hydroxyl group is a polyol for polyurethane foam, a urethane-based sealing agent. Polyols for urethane, polyol components for urethane adhesives, polyol components for urethane elastomers, binder components for urethane paints, primer components and sealer components, ink varnish components, polyurethane flame retardants and the like.

  And it can be set as a novel polyurethane by making the chlorinated polyether copolymer of this invention, various polyisocyanate compounds, and (with a chain extender as needed) react.

  As the above-mentioned polyisocyanate compound, any compound having two or more isocyanate groups can be used, and is not particularly limited. For example, 2,4-tolylene diisocyanate, 2,6 -Tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, 1,6-hexamethylene diisocyanate, , 4′-cyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, Examples thereof include 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, and a mixture of two or more thereof. Furthermore, modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, isocyanurate group, amide group, imide group, uretonimine group, uretdione group or oxazolidone group-containing modified product) are also included. Is done.

  Any chain extender may be used as long as it corresponds to the concept of polyurethane chain extender. The chain extender is preferably a low molecular compound having two or more active hydrogen groups. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6 -Diols such as hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, hydroquinone diethylol ether; ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, Cyclohexylenediamine, piperazine, tolylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, xylylenediamine, hydrogenated 4,4'-diaminodiphenylmethane, hydrogenated xylylenediamine Down, isophorone diamine, diamines such as norbornane diamine, and and a mixture of two or more thereof.

  In addition, the chlorinated polyether of the present invention can be used as a urethane raw material by mixing with other polyols. As the polyol at this time, those usually used for polyurethane can be used. For example, polyether polyols obtained by ring-opening polymerization of alkylene oxide, polymer polyols obtained by radical polymerization of vinyl monomers in polyether polyols, polyesters obtained by polycondensation of polyhydric alcohols and polycarboxylic acids Polyols, polyester amide polyols obtained by polycondensation of polyhydric alcohols, polycarboxylic acids and amino alcohols, polylactone polyols obtained by ring-opening polymerization of lactones, polyhydric alcohols and carbonates Polycarbonate polyols, acrylic polyols, polybutadiene polyols and hydrogenated products thereof, polyisoprene polyols and hydrogenated products thereof, partially saponified ethylene-vinyl acetate copolymers, soybean oil and castor Natural oil-based polyols such as oil, etc. can be mentioned.

EXAMPLES Hereinafter, although an Example demonstrates this invention, a present Example does not restrict | limit this invention at all.

<Analysis conditions>
~ Measurement of NMR spectrum ~
Measurement was performed in deuterated chloroform using a nuclear magnetic resonance spectrum measuring apparatus (manufactured by JEOL Ltd., GSX270WB).

~ Viscosity measurement ~
The steady flow viscosity was measured at 25 ° C. using a viscoelasticity measuring device (manufactured by Anton Paar, MCR-300).

~ Measurement of thermal decomposition temperature (TG / DTA) ~
Using a differential thermothermal weight simultaneous measurement device (TG / DTA6200 manufactured by SII Nano Technology Co., Ltd.), the temperature increase rate was 10 ° C./min, and the 1% weight loss temperature in air was measured.

~ Chlorine content ~
The sample was processed by the flask combustion method, and the amount of chlorine in the solution was calculated by titration with a mercuric nitrate solution.

~ Hydroxyl value ~
It measured according to the method of JISK1557-1.

~ PH measurement ~
It measured according to the method of JISK1557-5. Further, the solution after measurement was allowed to stand at room temperature for 48 hours and remeasured.

~ Solvent solubility ~
The solubility of the polyol was visually confirmed under the condition that the polyol concentration in the organic solvent was 10% by weight.

Example 1.
A 500 ml four-necked flask equipped with a stirring blade, a thermometer, a dropping funnel, and a nitrogen inlet tube was dried by heating under reduced pressure and purged with nitrogen, followed by 15.2 g (200 mmol) of propylene glycol as a polymerization initiator and an acid catalyst 5.7 g of boron trifluoride ether complex was charged, and the internal temperature was controlled at 40 ° C. with a water bath. After charging a mixture of 71.9 g (510 mmol) of 3,4-dichloro-1,2-epoxybutane and 133.5 g (947 mmol) of 1,4-dichloro-2,3-epoxybutane over 2 hours from a dropping funnel Further, a polymerization reaction was carried out at 40 ° C. for 4 hours. The reaction was followed by gas chromatography, and the conversion rates of 3,4-dichloro-1,2-epoxybutane and 1,4-dichloro-2,3-epoxybutane were 100% and 90%, respectively.

Next, 200 g of methylene chloride and 100 ml of 1% aqueous sodium hydroxide solution were added and stirred for 30 minutes. After oil-water separation, the organic layer was dried over anhydrous sodium sulfate, and anhydrous sodium sulfate and methylene chloride were removed to obtain 210 g of a viscous liquid. From ¹ H-NMR measurement, the viscous liquid was found to have 1.2 ppm of methyl group of propylene glycol, 3.4 to 4.4 ppm of methylene and methine of propylene glycol, and 3,4-dichloro-1,2-epoxybutane. Cyclized methylene and methine and 1,4-dichloro-2,3-epoxybutane ring-opened methylene and methine protons are observed, and the viscous liquid is opened with 3,4-dichloro-1,2-epoxybutane. It was confirmed that this was a chlorinated polyether copolymer of ring residue / 1,4-dichloro-2,3-epoxybutane ring-opened residue = 37/63 (molar ratio).

The obtained copolymer has a chlorine content of 46% by weight, a hydroxyl value of 110, a viscosity of 5.2 × 10 ⁵ mPa · s, and is soluble in methylene chloride, chloroform, acetone, dimethylformamide and 2-propanol. there were. The 1% weight loss temperature in air was 165 ° C. The pH immediately after synthesis was 4.8, and the pH after 48 hours was 4.6.

Example 2
In the method of Example 1, polymerization was carried out using 87.6 g (947 mmol) of epichlorohydrin instead of 1,4-dichloro-2,3-epoxybutane. Epichlorohydrin is consumed in its entirety, and chlorinated poly (ring-opening residue of 3,4-dichloro-1,2-epoxybutane / ring-opening residue of epichlorohydrin = 35/65 (molar ratio)). An ether copolymer was obtained.

The copolymer had a chlorine content of 40% by weight, a hydroxyl value of 130, a viscosity of 9.7 × 10 ⁴ mPa · s, and was soluble in methylene chloride, chloroform, acetone, dimethylformamide, and 2-propanol. The 1% weight loss temperature in air was 167 ° C. The pH immediately after the synthesis was 5.1, and the pH after 48 hours was 5.0.

Example 3
A 300 ml four-necked flask equipped with a stirring blade, thermometer, dropping funnel, and nitrogen inlet tube was dried by heating under reduced pressure and purged with nitrogen. Then, 68 g of methylene chloride and a bifunctional polypropylene glycol having a hydroxyl value of 560 as a polymerization initiator 13.9 g and 1.0 g of boron trifluoride ether complex as an acid catalyst were charged, and the internal temperature was controlled at 20-25 ° C. with a water bath. After charging 55.0 g (390 mmol) of 3,4-dichloro-1,2-epoxybutane over 50 minutes from the dropping funnel, a polymerization reaction was further performed at 20 to 25 ° C. for 2 hours. The reaction was followed by gas chromatography, and the conversion of 3,4-dichloro-1,2-epoxybutane was 100%.
Next, 100 ml of 1% aqueous sodium hydroxide solution was added and stirred for 30 minutes. After oil-water separation, the organic layer was dried over anhydrous sodium sulfate, and anhydrous sodium sulfate and methylene chloride were removed to obtain 63 g of a viscous liquid. From the ¹ H-NMR measurement of the viscous liquid, it was confirmed that 3,4-dichloro-1,2-epoxybutane was ring-opened, and the ring-opened product of 3,4-dichloro-1,2-epoxybutane It was confirmed that this was a chlorinated polyether copolymer of residue / propylene oxide ring-opened residue = 62/38 (molar ratio). The obtained copolymer has a chlorine content of 40% by weight, a hydroxyl value of 108, a viscosity of 6.1 × 10 ⁴ mPa · s, and is soluble in methylene chloride, chloroform, acetone, dimethylformamide and 2-propanol. there were. The 1% weight loss temperature in air was 170 ° C. The pH was 5.2 immediately after synthesis and 48 hours later.

Example 4
In the method of Example 3, the polymerization initiator was changed to 26.1 g of a bifunctional polypropylene glycol having a hydroxyl value of 280, and 38.6 g (274 mmol) of 3,4-dichloro-1,2-epoxybutane. 60 g was obtained. The viscous liquid was a chlorinated polyether copolymer of 3,4-dichloro-1,2-epoxybutane ring-opened residue / propylene oxide ring-opened residue = 38/62 (molar ratio). . The obtained copolymer has a chlorine content of 30% by weight, a hydroxyl value of 105, a viscosity of 6.8 × 10 ³ mPa · s, and is soluble in methylene chloride, chloroform, acetone, dimethylformamide and 2-propanol. there were. The 1% weight loss temperature in air was 175 ° C. The pH was 5.5 immediately after synthesis and 48 hours later.

Example 5 FIG.
A 500 ml four-necked flask equipped with a stirring blade, a thermometer, a dropping funnel, and a nitrogen introduction tube was dried by heating under reduced pressure and purged with nitrogen, and then 100 g of a bifunctional polypropylene glycol having a hydroxyl value of 122 as a polymerization initiator, As above, 1.0 g of boron trifluoride ether complex was charged, and the internal temperature was controlled at 20 to 25 ° C. with a water bath. After charging 55.0 g (390 mmol) of 3,4-dichloro-1,2-epoxybutane over 50 minutes from the dropping funnel, a polymerization reaction was further performed at 20 to 25 ° C. for 2 hours. The reaction was followed by gas chromatography, and the conversion of 3,4-dichloro-1,2-epoxybutane was 100%. Post-treatment was performed in the same manner as in Example 1 to obtain 148 g of a viscous liquid. The viscous liquid is 3,4-dichloro-1,2-epoxybutane ring-opened residue / propylene oxide ring-opened residue = 18/82 (molar ratio) chlorinated polyether copolymer. It was confirmed. The resulting copolymer has a chlorine content of 18% by weight, a hydroxyl value of 75, and a viscosity of 1.1 × 10 ³ (mPa · s), which is suitable for methylene chloride, chloroform, acetone, dimethylformamide, and 2-propanol. It was melted. The 1% weight loss temperature in air was 178 ° C. The pH was 5.8 immediately after synthesis and 48 hours later.

Example 6
In the method of Example 5, the polymerization was carried out by changing the amount of the polymerization initiator to 200 g to obtain 238 g of a viscous liquid. The viscous liquid was a chlorinated polyether copolymer of 3,4-dichloro-1,2-epoxybutane ring-opened residue / propylene oxide ring-opened residue = 10/90 (molar ratio). . The resulting copolymer has a chlorine content of 11% by weight, a hydroxyl value of 95, and a viscosity of 6.2 × 10 ² (mPa · s), which is suitable for methylene chloride, chloroform, acetone, dimethylformamide, and 2-propanol. It was melted. The 1% weight loss temperature in air was 177 ° C. The pH was 6.1 immediately after synthesis and 48 hours later.

Example 7
In the method of Example 5, the polymerization initiator was changed to 200 g of a bifunctional polypropylene glycol having a hydroxyl value of 28 to perform polymerization, and 232 g of a viscous liquid was obtained. The viscous liquid was a chlorinated polyether copolymer of 3,4-dichloro-1,2-epoxybutane ring-opened residue / propylene oxide ring-opened residue = 10/90 (molar ratio). . The obtained copolymer has a chlorine content of 11% by weight, a hydroxyl value of 24, a viscosity of 2.2 × 10 ³ (mPa · s), and is soluble in methylene chloride, chloroform, acetone, dimethylformamide, and 2-propanol. Met. The 1% weight loss temperature in air was 175 ° C. The pH was 6.2 immediately after synthesis and 48 hours later.

Example 8 FIG.
In the method of Example 5, the polymerization initiator was changed to a trifunctional polypropylene glycol glycerin ether having a hydroxyl value of 160 to perform polymerization, and 136 g of a viscous liquid was obtained. The viscous liquid was a chlorinated polyether copolymer of 3,4-dichloro-1,2-epoxybutane ring-opened residue / propylene oxide ring-opened residue = 20/80 (molar ratio). . The obtained copolymer has a chlorine content of 18% by weight, a hydroxyl value of 96, and a viscosity of 3.5 × 10 ³ (mPa · s), which is suitable for methylene chloride, chloroform, acetone, dimethylformamide and 2-propanol. It was melted. The 1% weight loss temperature in air was 170 ° C. The pH was 5.7 immediately after synthesis and 48 hours later.

Example 9
A 500 ml four-necked flask equipped with a stirring blade, a thermometer, a dropping funnel, and a nitrogen introduction tube was dried by heating under reduced pressure and purged with nitrogen, followed by 15.2 g (200 mmol) of propylene glycol as a polymerization initiator and 30 g of methylene chloride. As an acid catalyst, 0.5 g of boron trifluoride ether complex was charged, and the internal temperature was controlled at 20 to 25 ° C. with a water bath. 5,6.4 g (400 mmol) of 3,4-dichloro-1,2-epoxybutane was charged from the dropping funnel over 30 minutes. Thereafter, 23.2 g (400 mmol) of propylene oxide was charged over 30 minutes, and the reaction was continued for 2 hours. The reaction was followed by gas chromatography, and the conversion rates of 3,4-dichloro-1,2-epoxybutane and propylene oxide were 100% each. It produced | generated by the method similar to Example 3, and obtained 85 g of viscous liquids. The viscous liquid was a chlorinated polyether copolymer of 3,4-dichloro-1,2-epoxybutane ring-opened residue / propylene oxide ring-opened residue = 40/60 (molar ratio). . The obtained copolymer has a chlorine content of 30% by weight, a hydroxyl value of 225, a viscosity of 2.0 × 10 ² (mPa · s), and is soluble in methylene chloride, chloroform, acetone, dimethylformamide, and 2-propanol. Met. The 1% weight loss temperature in air was 162 ° C. The pH was 5.4 immediately after synthesis and 48 hours later.

Example 10
In the method of Example 9, the amount of propylene oxide was changed to 46.4 g (800 mmol), and polymerization was performed to obtain 104 g of a viscous liquid. The viscous liquid was a chlorinated polyether copolymer of 3,4-dichloro-1,2-epoxybutane ring-opened residue / propylene oxide ring-opened residue = 29/71 (molar ratio). . The obtained copolymer has a chlorine content of 24% by weight, a hydroxyl value of 182 and a viscosity of 1.2 × 10 ² mPa · s, and is soluble in methylene chloride, chloroform, acetone, dimethylformamide and 2-propanol. there were. The 1% weight loss temperature in air was 164 ° C. The pH was 5.5 immediately after synthesis and 48 hours later.

  Table 1 shows the composition of each structural unit in the polymers obtained in Examples 1 to 10.

比較例１．
実施例１と同様の装置を使用し、３，４−ジクロロ−１，２−エポキシブタンの重合を実施した。重合開始剤としてプロピレングリコール５．０ｇ（６３ｍｍｏｌ）、酸触媒として三フッ化ホウ素エーテル錯体１．０ｇ、重合溶媒として塩化メチレン６０．０ｇを仕込み、内温を２０℃とした。３，４−ジクロロ−１，２−エポキシブタン６３．０ｇ（４４７ｍｍｏｌ）を滴下ロートより３時間かけて仕込んだ後、さらに２０℃で１時間重合反応を行った。実施例１と同様に重合後の処理を行い、粘性液体６５ｇを得た。^１Ｈ−ＮＭＲより該粘性液体は３，４−ジクロロ−１，２−エポキシブタンが開環重合した塩素化ポリエーテルであることを確認した。得られた重合体の塩素含量は４６重量％、水酸基価は１１０、粘度は１．１×１０^６ｍＰａ・ｓあり、塩化メチレン、クロロホルム、アセトン、ジメチルホルムアミド、２−プロパノールに可溶であった。また、空気中での１％重量減少温度は１７０℃を示した。合成直後のｐＨは４．９であったが、空気中４８時間後のｐＨは４．２に低下した。

Comparative Example 1
Using the same apparatus as in Example 1, 3,4-dichloro-1,2-epoxybutane was polymerized. As a polymerization initiator, 5.0 g (63 mmol) of propylene glycol, 1.0 g of boron trifluoride ether complex as an acid catalyst, and 60.0 g of methylene chloride as a polymerization solvent were charged, and the internal temperature was set to 20 ° C. After charging 63.0 g (447 mmol) of 3,4-dichloro-1,2-epoxybutane over 3 hours from the dropping funnel, a polymerization reaction was further performed at 20 ° C. for 1 hour. The post-polymerization process was performed in the same manner as in Example 1 to obtain 65 g of a viscous liquid. ^{From 1} H-NMR, it was confirmed that the viscous liquid was a chlorinated polyether obtained by ring-opening polymerization of 3,4-dichloro-1,2-epoxybutane. The obtained polymer had a chlorine content of 46% by weight, a hydroxyl value of 110, a viscosity of 1.1 × 10 ⁶ mPa · s, and was soluble in methylene chloride, chloroform, acetone, dimethylformamide and 2-propanol. . The 1% weight loss temperature in air was 170 ° C. The pH immediately after the synthesis was 4.9, but the pH after 48 hours in the air dropped to 4.2.

  The polymer consisting only of the structural unit A obtained in Comparative Example 1 was highly viscous and difficult to handle.

Comparative Example 2
Using the same apparatus as in Example 1, 9.3 g (122 mmol) of propylene glycol as a polymerization initiator and 4.2 g of boron trifluoride ether complex as an acid catalyst were charged, and the internal temperature was set to 40 ° C. After charging 140 g (993 mmol) of 1,4-dichloro-2,3-epoxybutane from the dropping funnel over 3 hours, a polymerization reaction was further performed at 40 ° C. for 7 hours. The post-polymerization process was performed in the same manner as in Example 1 to obtain 115 g of a viscous liquid. ^{From 1} H-NMR, it was confirmed that the viscous liquid was a chlorinated polyether obtained by ring-opening polymerization of 1,4-dichloro-2,3-epoxybutane. The obtained polymer had a chlorine content of 46% by weight, a hydroxyl value of 110, a viscosity of 1.0 × 10 ⁶ mPa · s and was soluble in acetone, but partially in methylene chloride, chloroform and dimethylformamide. Insoluble, insoluble in 2-propanol. The 1% weight loss temperature in air was 175 ° C. The pH was not measurable because it was insoluble in a given solvent.

  The polymer consisting only of the structural unit B obtained in Comparative Example 2 had high viscosity and was difficult to handle, and had low solvent solubility.

Comparative Example 3
A temperature at which carbon tetrachloride is gently refluxed after charging 20 g of bifunctional polypropylene glycol having a hydroxyl value of 280 and 500 ml of carbon tetrachloride into a 1000 ml four-necked flask equipped with a stirrer, thermometer, cooling pipe, and chlorine gas introduction pipe. The chlorination reaction was carried out by blowing chlorine gas while irradiating ultraviolet rays. The reaction solution was taken out as appropriate, and the reaction was terminated when the chlorination rate reached 20%. Carbon tetrachloride was removed under reduced pressure to obtain 32 g of chlorinated polypropylene glycol. The obtained chlorinated polypropylene glycol was soluble in methylene chloride, chloroform, acetone, dimethylformamide and 2-propanol, and the 1% weight loss temperature in air was 92 ° C. Moreover, although pH immediately after the synthesis was 5.7, the pH after 48 hours in the air decreased to 4.8.

  The polymer having no structural unit A obtained in Comparative Example 3 had poor thermal stability and was likely to cause dehydrochlorination.

Claims (4)

Following formula (1)

And a structural unit A represented by the following formula (3)

[In the above formula (3), R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms not containing a halogen atom, or a carbon not containing a halogen atom. The aryl group of several 6-10 is represented. ]
A chlorinated polyether copolymer containing the structural unit C represented by the formula (1), containing 5 to 90 mol% of the structural unit A, and having a viscosity at 25 ° C. of 10 ² to 10 ⁵ mPa · s. A chlorinated polyether copolymer. The chlorinated polyether copolymer according to claim 1, which has a hydroxyl value of 1 to 1000 (mgKOH / g). It is characterized by ring-opening copolymerization of 3,4-dichloro-1,2- epoxybutane and alkylene oxide having 2 to 20 carbon atoms in the presence of an acid catalyst using an active hydrogen-containing compound as a polymerization initiator. The manufacturing method of the chlorinated polyether copolymer of Claim 1 or 2 . The method for producing a chlorinated polyether copolymer according to claim 3 , wherein the active hydrogen-containing compound is a polyether polyol having a hydroxyl value of 120 to 1500 (mgKOH / g).