JPS6335170B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new method for producing polyurethane. Self-emulsification is achieved by introducing hydrophilic groups such as tertiary amino groups, carboxyl groups, and sulfonic acid groups into the polyurethane resin, or by increasing the hydrophilicity of the polyurethane resin itself by using a hydrophilic polyol such as polyethylene glycol as the polyol. It is known to produce polyurethane emulsions of high quality. In these production methods, diisocyanate difunctional compounds with a molecular weight of 300% are generally used in an organic solvent.
The above polyalkylene oxide or polyester polyol is reacted to produce a prepolymer with terminal NCO groups, and this is combined with a chain extender having a hydrophilic group in the molecule and two active hydrogens at the terminal that reacts with the NCO group. A polyurethane emulsion is produced by reacting the above-described polyurethane resin with the chain extender to form a polyurethane resin, and forcefully emulsifying the polyurethane resin in water containing an acid or base that forms a salt with the hydrophilic group in the chain extender. However, in the above method, the organic solvent used as a solvent during the synthesis of polyurethane resin must be removed eventually, and various extra steps are required in terms of operational safety and hygiene. However, at present, polyurethane having cationic groups has not been obtained without using the above-mentioned organic solvent. An object of the present invention is to provide a method for producing self-emulsifying polyurethane without using any organic solvent. The present invention uses a polyurethane formed from an organic polyisocyanate (A), a polyol, and a chain extender (C) having at least one tertiary amino group and two or more active hydrogens in the molecule as an ethylenically unsaturated compound. The present invention relates to a method for producing polyurethane, which comprises treating with a quaternizing agent (E) in the presence of (D). Furthermore, the present invention provides an ethylenically unsaturated compound (B') having active hydrogen together with the polyol (B).
It also relates to a method for producing polyurethane that uses the same method. In addition, when the latter compound (B) and compound (B') are used together, in addition to the NCO-terminated prepolymer obtained from polyisocyanate (A) and polyol (B), high-molecular-weight and untreated intermediates may be used. The isocyanate of the reaction is always included, so next compound (B′)
When the reaction is carried out by adding polyisocyanate
Intermediates obtained from (A) and compound (B') are also included. The polyurethane of the present invention can be used, for example, in adhesives, paints,
It is useful as a film forming agent, fiber/leather treatment agent, etc. Organic polyisocyanate (A) used in the present invention
Examples of the diisocyanate include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), tolidine diisocyanate (TODI), xylylene diisocyanate (XDI), naphthylene diisocyanate (MDI), and isophorone diisocyanate ( IPDI),
Hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI)
and polyisocyanates such as triphenylmethane triisocyanate and polymethylene polyphenyl isocyanate (PAPI). It is also possible to use a part of these isocyanates blocked with a blocking agent. In the present invention, various polyester polyols, polyether polyols, and other polyols can be used as the polyol (B). Examples of polyester polyols include aliphatic dicarboxylic acids having 4 to 20 carbon atoms such as adipic acid, suberic acid, sebacic acid, and brassylic acid, terephthalic acid, and isophthalic acid as acid components, and ethylene glycol, propylene glycol, neopentyl glycol, 1 or more carbon atoms such as hexamethylene glycol
6 aliphatic diols, ether glycols such as diethylene glycol, dipropylene glycol,
Polyester polyols or polycaprolactone polyols containing spiroglycols, N-alkyl dialkanolamines such as N-methyldiethanolamine, etc. as polyol components can be used, and specific examples include polyethylene adipate polyol, polybutylene adipate polyol, and polyethylene. Adipate polyols such as propylene adipate polyol, terephthalic acid polyols (e.g., Toyobo Co., Ltd., product names Vylon RUX, Vylon RV-200L), polycaprolactone polyols (e.g., Daicel Chemical, product names Plaxel 212, Plaxel 220), etc. I can give an example. Specific examples of polyether polyols include polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene polyol, and the like. In addition, other polyols include polycarbonate polyols (e.g., West Germany, Bayer AG, product name Desmofene 2020E), polybutadiene polyols (e.g., Nippon Soda, product names G-1000, G-
2000, G-3000, Idemitsu Petrochemical, product name Poly bd
R-45 HT), polypentanediene polyol,
Examples include castor oil-based polyols. In the present invention, an ethylenically unsaturated compound (B)' having active hydrogen can be used together with the polyol (B). Various types of ethylenically unsaturated compounds (B)′ having active hydrogen can be used, but representative examples include ethylene glycol,
Propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, mono(meth)acrylate of dihydric alcohol such as polypropylene glycol, trimethylolethane , mono- and di(meth)acrylates of trihydric alcohols such as trimethylolpropane and glycerin, and di- and tri(meth)acrylates of tetrahydric or higher alcohols such as pentaerythritol. As the chain extender (C) in the present invention, a chain extender having at least one tertiary amino group and two or more active hydrogens in the molecule is used. Examples of the above chain extenders include N-methyldiethanolamine, N-ethyldiethanolamine,
Examples include N-butyldiethanolamine, bis-hydroxyethylpiperazine, and N-phenyldiethanolamine. Further, in the present invention, ordinary chain extenders can be used in combination in addition to the chain extender (C), and preferable examples include those having the general formulas HO―R ¹ -OH, H ₂ N―R ² -NH ₂ , A(―CH ₂ CH ₂ OH) ₂ , H ₂ N—B—NH ₂ , (R ¹ is a linear or branched alkylene group having 2 to 10 carbon atoms, and may be connected via an oxygen atom. R ² is a linear or branched alkylene group or alicyclic group having 2 to 10 carbon atoms.A and B are groups having an aromatic ring.) Aliphatic diol, aliphatic diamine, aromatic diol represented by , aromatic diamines, and the like. Preferred examples of the aliphatic diol include ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, etc., and specific examples of the aliphatic diamine include ethylene diamine, 1,6
-Hexamethylene diamine, isophorone diamine, etc. Further, as A of the above aromatic diol, for example,

【formula】

【formula】

【formula】

【formula】

[Formula] etc. can be exemplified, and as B of aromatic diamine,

【formula】

【formula】

[Formula] etc. can be exemplified. In the present invention, the chain extender (C) having at least one tertiary amino group and two or more active hydrogens in the molecule can be treated with a quaternizing agent in advance, or the chain extender It is also possible to copolymerize (C) into polyurethane and then treat it with a quaternizing agent. In the present invention, the treatment with the quaternizing agent is carried out in the presence of the ethylenically unsaturated compound (D). Various known compounds can be used as the ethylenically unsaturated compound (D), but the reaction is usually carried out.
Preferably, it is liquid in the range of 40 to 100°C.
Typical examples include styrene, vinyltoluene, chlorostyrene, t-butylstyrene, α-
Methylstyrene, divinylbenzene, acrylic acid, methacrylic acid, methyl, ethyl, isopropyl, n-butyl, t-butyl, α-ethylhexyl, n-nonyl, n-decyl, lauryl, stearyl ester of acrylic acid or methacrylic acid, etc. n-Butoxyethyl, cyclohexyl, phenoxyethyl, tetrahydrofurfuryl, glycidyl, allyl, benzyl, tribromophenyl, 2,3-dichloropropyl, 3-chloro-2-hydroxypropyl, N,N- of acrylic acid or methacrylic acid dimethylaminoethyl, N,N
- Diethylaminoethyl, Nt-butylaminoethyl ester, etc., ethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, molecular weight (hereinafter MW)
) 200-1000 polyethylene glycol mono(meth)acrylate, MW200-1000 polyethylene glycol monomethyl ether mono(meth)acrylate, MW200-1000 polypropylene glycol mono(meth)acrylate,
Polypropylene glycol monomethyl ether mono(meth)acrylate with MW200~1000,
Polyethylene glycol monoethyl ether mono(meth)acrylate with MW200~1000,
MW200-1000 polypropylene glycol monoethyl ether mono(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3
-Propanediol (meth)acrylate, 1,
4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate,
1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerin di(meth)acrylate,
Glycerin tri(meth)acrylate, trimethylolethane di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, diallyl phthalate, triallyl isocyanurate, dibutyl fumarate, vinyl acetate, etc. Can be mentioned. However, if present during the urethanization reaction, ethylenically unsaturated compounds having active hydrogen should be excluded from the above. These ethylenically unsaturated compounds (D) are usually polyurethane 100
It is preferable to add about 5 to 200 parts per part (by weight, hereinafter the same), and within this range, effects such as lowering of viscosity are large, and a polyurethane having desired properties can be obtained. Here, the compound (D) can be the same as the compound (B)'. Compound (D) and/or compound (B)' can be used alone or in combination of two or more. Furthermore, when using compound (D) and/or compound (B)', a polymerization inhibitor can be added if necessary. As a polymerization inhibitor, benzoquinone,
Examples include 2,5-diphenyl-p-benzoquinone, hydroquinone, mono-t-butylhydroquinone, hydroquinone monomethyl ether, β-naphthol, catechol, pyrogallol, etc., and these are based on the total amount of compounds having ethylenically unsaturated bonds. It is desirable to add about 0.005 to 1% by weight. In the present invention, the quaternizing agent (E) includes, for example, dialkyl sulfates such as dimethyl sulfate and diethyl sulfate, alkyl halides such as ethyl bromide, methyl chloride, and methyl iodide, and various alkylating agents such as benzyl chloride. Can be used. The polyurethane of the present invention can be obtained by various methods. For example, organic polyisocyanates
(A), a method of synthesizing urethane from a polyol (B) and a chain extender (C), and then adding and reacting an ethylenically unsaturated compound (D) and a quaternizing agent (E), (A) to ( A method in which the three components of C) are subjected to a urethanization reaction in the presence of (D), and then treated with (E), a terminal NCO prepolymer is synthesized from (A) and (B), while (C) to (E A method of synthesizing a chain extender that has been previously treated with a quaternizing agent from component ) and reacting the two; a method of synthesizing a terminal NCO prepolymer from (A) and (C) and reacting it with (B); Then, a method of treating with (E) in the presence of (D), or adding (D) and (E) to the terminal NCO prepolymer from (A) and (C) above,
Examples include a method in which (B) is then added and reacted. Furthermore, when an ethylenically unsaturated compound (B)' having active hydrogen is used together with (B), the reaction can be carried out in the same manner. In the present invention, the ratio of each component can be appropriately determined from a wide range depending on the target polyurethane, but usually the active hydrogen contained in the polyol (B), chain extender (C) and/or compound (B)' group and compound (A)
The chemical equivalent ratio of NCO groups is 0.9-1.4, preferably 0.95
-1.1, and the reaction is usually carried out at 30-130°C, preferably 40-120°C. Further, the treatment with the quaternizing agent of the present invention is usually 40
It is preferable to carry out at a temperature in the range of ~100°C. The polyurethane of the present invention can be further cured by heat and/or light by adding a known radical polymerization initiator if necessary. Various radical polymerization initiators can be used, but typical examples include benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoyl peroxide, azobisisobutyronitrile, etc. One type or a mixture of two or more types can be used. It can be used as The radical polymerization initiator is about 0.01 to 10% by weight, preferably about 0.05 to 5% by weight, based on the total amount of polyurethane and ethylenically unsaturated compound.
It can be added within the following range. As described above, in the present invention, it is possible to produce polyurethane treated with a quaternizing agent using a self-reactive ethylenically unsaturated compound (D) as a solvent without using a solvent such as an organic solvent to be removed. can. Further, when a water-soluble ethylenically unsaturated compound is used, a polyurethane emulsion can be obtained by simply adding and mixing the polyurethane of the present invention in water. In addition, when the above emulsion is used as an adhesive, the temperature is generally well over 100°C.
For example, a method of curing at 160°C is employed, and since the ethylenically unsaturated compound (D) is also reacted and cured at the same time, various properties can be further improved. As described above, since the polyurethane of the present invention has been treated with a quaternizing agent, it is presumed to have cationic properties, although this has not been clearly confirmed. A detailed explanation will be given below with reference to examples. Example 1 (a) Nituporan 4009 (polybutylene adipate diol, molecular weight 1000, manufactured by Nippon Polyurethane Co., Ltd.)
(b) 75 g of MDI, (c) 10.7 g of N-methyldiethanolamine, (d) 5.4 g of 1,4-butanediol, (e) 11.3 g of dimethyl sulfate, (a) and () in a reactor equipped with a stirring device. b) Add the ingredients,
The reaction was carried out at 80°C for 1 hour. Next, 108.2 g of tetrahydrofurfuryl acrylate was added, components (c) and (d) were added, and NCO was measured by infrared absorption spectrum (IR).
After reacting for about 1 hour and 20 minutes until no absorption of polyurethane was detected, the mixture was cooled to 70°C, component (e) was added, and stirred for about 30 minutes to obtain a solution () containing 70% by weight of polyurethane. Example 2 (a) 2,4-TDI 312.2g (b) 2-hydroxyethyl acrylate 208.2g (ethylene glycol monoacrylate) (c) Dibutyltin dilaurate 0.052g Component (a) was placed in a reactor equipped with a stirring device, and the mixture was heated to 50 g. After heating to ℃ and adding the mixture of components (b) and (c) dropwise over 2 hours and 20 minutes while maintaining this temperature, OH
The reaction was allowed to proceed for approximately 1 hour and 50 minutes until no absorption was detected, yielding an intermediate (P ₁ ). (d) 2,4-TDI 386.9g (e) PEG-1000 1123.8g (f) Dibutyltin dilaurate 0.15g After placing component (d) in a separate reactor equipped with a stirring device and heating to 70℃, (e) A mixture of components (f) and (f) was gradually added, and the mixture was reacted for about 2 hours and 40 minutes until no OH absorption was detected by IR to obtain an intermediate (P ₂ ). Then (g) Intermediate (P ₁ ) 544.7 g (h) Intermediate (P ₂ ) 1394.4 g (i) N-methyldiethanolamine 234.0 g (j) Dimethyl sulfuric acid 208.8 g Into a new reactor with stirring device (g) Add component (h) and heat to 50℃, then add component (i) while maintaining this temperature and react for 2 hours and 30 minutes until no NCO absorption is detected by IR, then add component (j). A mixture of 595.5 g of tetrahydrofurfuryl acrylate and 595.5 g of tetrahydrofurfuryl acrylate was gradually added, and after the addition, the reaction was continued for another 30 minutes to obtain a solution (2) containing 80% by weight of polyurethane having cationic groups. Example 3 (a) Byron RV200L (polyester diol,
(molecular weight 1860, manufactured by Toyobo Co., Ltd.) 280 g (b) PTMG1000 (polytetramethylene glycol, molecular weight 1000, manufactured by Mitsubishi Chemical Corporation) 120 g (c) 2,4-TDI 101.7 g (d) N-ethyldiethanolamine 30.4 g (e) Bisphenol A 13.6g (f) Dimethyl sulfate 28.8g Components (a), (b) and (c) were placed in a reactor equipped with a stirring device and reacted at 80°C for 1.5 hours. Next, 152.9 g of tetrahydrofurfuryl acrylate was added, components (d) and (e) were added, and the reaction was continued for another 1 hour and 40 minutes until no NCO absorption was detected in the infrared absorption spectrum (IR). 230.1 g of ethyl acrylate was added, the mixture was cooled to 70°C, and component (f) was added and stirred for about 30 minutes to obtain a solution (2) containing 60% by weight of polyurethane. Example 4 (a) MDI 313.4g (b) PEA1000 (polyethylene glycol adipate) 852.5g (c) PBG1000 (polybutadiene glycol)
401.1g (d) Hydroxyethyl methacrylate 81.5g (e) Dibutyltin dilaurate 0.18g Place components (a), (b), and (c) in a reactor equipped with a stirring device.
The reaction was carried out at 80°C for about 2 hours. Next, a mixture of components (d) and (e) was gradually added dropwise, and the mixture was further reacted for 1.5 hours to obtain an intermediate (P ₃ ). Then (g) Intermediate (P ₁ ) 680.4 g (h) Intermediate (P ₃ ) 77.1 g (i) N-methyldiethanolamine 32.8 g (j) Dimethyl sulfate 31.0 g Into a new reactor with stirring device (g) Add component (h) and heat to 50℃, then add component (i) while maintaining this temperature and react for 2 hours and 20 minutes until no NCO absorption is detected by IR, then add component (j). A mixture of 312.4 g of hydroxyethyl methacrylate and 129.8 g of tetrahydrofurfuryl acrylate was gradually added and allowed to react for an additional 30 minutes to obtain a solution containing 65 wt % of polyurethane having cationic groups. Test (1) Add 3.0wt% of azobisisobutyronitrile to the solution (), apply it to a thickness of 50μ on an iron plate according to the usual curing method for polyurethane solutions, and heat it at 160℃ for 3 minutes. As a result, it became completely dry, and it was confirmed that all the components had undergone a curing reaction and the reaction had been completed. Test (2) 2.5g of benzoin methyl ether was added to 100g of the solution (), and this was applied to a thickness of 50μ on an iron plate, and when irradiated with a 1KW high-pressure mercury lamp at an irradiation distance of 30cm for 15 seconds, the coating film was completely coated. The state of hardening and drying is shown. Test (3) When 100 g of the solution () was gradually poured into 400 g of water and thoroughly stirred with a homomixer, a uniform emulsion with a solid content of 20 wt% was obtained. Test (4) When 3.0wt% of methyl ethyl ketone peroxide was added to the solution () and heated at 120℃ for 5 minutes in the same manner as in test (1), the solution became completely dry and all components underwent a curing reaction. It was confirmed that the reaction was completed. Test (5) When 100 g of the solution () was gradually poured into 400 g of water and thoroughly stirred with a homomixer, a milky white and uniform emulsion with a solid content of 20 wt% was obtained. Test (6) When irradiated with ultraviolet rays in the same manner as in Test (2), the coating film was completely cured and dried. Test (7) When 100 g of solution () was gradually poured into 400 g of water and thoroughly stirred with a homomixer, a milky white and uniform emulsion with a solid content of 20 wt% was obtained. Test (8) When the solution () was treated in the same manner as in test (7), a milky white and uniform emulsion was obtained like the solution (). Test (9) For comparison, solutions () to () were prepared in the same manner without adding the quaternizing agent.
When the polyurethane component was synthesized and tested in water, the polyurethane component coagulated and precipitated and did not form an emulsion.

Claims (1)

[Claims] 1. A polyisocyanate (A), a polyol (B), and a chain extender (C) having at least one tertiary amino group and two or more active hydrogens in the molecule. Polyurethane as an ethylenically unsaturated compound (D)
A method for producing polyurethane, which comprises treating with a quaternizing agent (E) in the presence of. 2 Organic polyisocyanate (A), polyol (B),
Ethylenically unsaturated compound with active hydrogen (B′)
Also, polyurethane formed from a chain extender (C) having at least one tertiary amino group and two or more active hydrogens in the molecule is an ethylenically unsaturated compound.
A method for producing polyurethane, which comprises treating with a quaternizing agent (E) in the presence of (D). 3. The manufacturing method according to claim 1 or 2, wherein the chain extender is treated with a quaternizing agent in advance.