JP2008255210A - Method for producing polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polymer in which odor is reduced by reducing odor generated during or after production of a polymer having an ester group and an amino group or its quaternary base in the molecule and to provide a polymer for fiber modification in which odor was reduced. <P>SOLUTION: In the method for producing a polymer having an ester group, an amino group or its quaternary base in the molecule, a monomer component containing a monomer having an ester group or a monomer having an amino group or it's quaternary base (wherein the monomer having the ester group and the monomer having the amino group or its quaternary base may be same monomers) is polymerized by using a hydroxy compound having ≥180°C boiling point as a solvent. The polymer for fiber modification is obtained by the production method. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a polymer with reduced odor, and a fiber-modifying polymer obtained by the production method.

  A polymer having an ester group and an amino group or a quaternary base thereof in a molecule is known as a polymer that is added to a detergent or a fiber treatment agent to modify a fiber. When an alcoholic solvent such as ethanol is used as a solvent in producing this polymer, the resulting polymer may feel an odor different from the alcoholic solvent (hereinafter sometimes referred to as a different odor). When the polymer thus obtained is added to a product such as a detergent or a fiber treatment agent, the odor of the product may be deteriorated.

Several methods for reducing odor when producing polymers have been proposed. For example, a method of reducing odor by distilling off unreacted monomers together with a solvent (Patent Document 1), a method of reducing odor by washing a polymer with water (Patent Document 2), and deodorizing a polymer with activated carbon or the like A method of reducing odor by treating with an agent or adding a deodorant such as activated carbon to the polymer (Patent Document 3), contacting the polymer with non-heated or heated inert gas or vapor under normal pressure or reduced pressure And deodorizing methods. However, it is difficult for any technique to perform complete deodorization, and the deodorization process is inefficient because it takes considerable time and cost. Further heating could cause new odors, which was a problem.
JP 2000-290306 A JP-A-2005-290213 JP 2000-319477 A

  An object of the present invention is to reduce the odor generated during or after the production of a polymer having an ester group and an amino group or its quaternary base in the molecule, and to produce a odor-reduced polymer, as well as It is to provide a reduced fiber modifying polymer.

  The present invention is a method for producing a polymer having an ester group and an amino group or a quaternary base thereof in a molecule, wherein a hydroxy compound having a boiling point of 180 ° C. or higher is used as a solvent, and a monomer having an ester group and an amino group or Monomer component containing a monomer having a quaternary base (however, a monomer having an ester group and an amino group or a monomer having a quaternary base may be the same monomer), a method for producing a polymer, and Provided is a fiber-modifying polymer obtained by the production method.

  According to the production method of the present invention, the amount of odorous substances produced during or after the production of a polymer having an ester group and an amino group or its quaternary base in the molecule is reduced to obtain a polymer with reduced odor. Can do. In addition, the polymer obtained by the present invention can be modified without contaminating the fiber by adding it to a detergent, a fiber treatment agent or the like, and is useful as a fiber modifying polymer.

[solvent]
The hydroxy compound used as a solvent in the production method of the present invention has a boiling point of 180 ° C. or higher, preferably 180 to 500 ° C., more preferably 180 to 400 ° C. Examples of the hydroxy compound used in the present invention include alkylene glycol or polyalkylene glycol (hereinafter referred to as (poly) alkylene glycol) monoether, polyol and the like.

  The (poly) alkylene glycol monoether is a monoalkyl of an alkylene group having 2 to 3 carbon atoms (poly) alkylene glycol (an alkyl group having 1 to 12, preferably 1 to 8 carbon atoms) or aryl (preferably phenyl). Ether. 1-50 are preferable and, as for the alkylene oxide average addition mole number of polyalkylene glycol, 2-3 are more preferable.

  Specific examples of (poly) alkylene glycol monoether include, for example, ethylene glycol monophenyl ether, polyethylene glycol monophenyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monopropyl ether, polyethylene glycol monoisopropyl ether, polyethylene glycol monobutyl ether, polyethylene glycol (Poly) ethylene glycol monoethers such as monoisobutyl ether, ethylene glycol monohexyl ether, polyethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, polyethylene glycol mono 2-ethylhexyl ether; propylene glycol monophenyl ether, polypropylene glycol Bruno phenyl ether, polypropylene glycol monomethyl ether, polypropylene glycol monopropyl ether, (poly) propylene glycol monomethyl ether and poly propyl glycol monobutyl ether.

  As the polyol, a divalent to tetravalent polyol is preferable. For example, a diol having 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, neopentylglycol; Examples include polyethylene glycol; polypropylene glycol such as dipropylene glycol and tripropylene glycol; cyclohexanedimethanol, trimethylolpropane, and the like.

  In the present invention, as the solvent, these hydroxy compounds having a boiling point of 180 ° C. or higher may be used alone, or two or more kinds thereof may be mixed and used.

  Among these solvents, (poly) ethylene glycol monoether or (poly) propylene glycol monoether, particularly monophenyl ether is preferred, (poly) ethylene glycol monoether is more preferred, ethylene glycol monophenyl ether, diethylene glycol monophenyl. (Poly) ethylene glycol monophenyl ether such as ether and triethylene glycol monophenyl ether is more preferred.

  Table 1 summarizes the boiling points of typical hydroxy compounds used as solvents in the present invention.

[Monomer component]
The monomer component used in the present invention contains a monomer having an ester group and a monomer having an amino group or its quaternary base, and the monomer having an ester group and the monomer having an amino group or its quaternary base are the same monomer. That is, it may be a monomer having an ester group and an amino group or a quaternary base thereof in the molecule.

  Among the monomers used in the present invention, monomers having an ester group and an amino group or its quaternary base in the molecule include (i) dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylamino (Meth) acryl having amino groups such as ethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate Acid ester, (ii) having a quaternary ammonium base obtained by quaternizing a (meth) acrylic acid ester having an amino group (i) with a quaternizing agent such as methyl chloride, dimethyl sulfate, or diethyl sulfate Acrylic ester and the like (i Preferred (meth) acrylic acid ester having an amino group is.

  In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, and “(meth) acrylate” means acrylate or methacrylate.

  Among the monomers used in the present invention, the monomer having only an ester group and not having an amino group or its quaternary base includes (iii) methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) ) Acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, oleyl (meth) acrylate and other (meth) acrylic acid ester having a C1-C22 hydrocarbon group, preferably an alkyl group or alkenyl group, ( iv (Meth) acrylic acid ester having a C1-C22 hydroxyalkyl group such as hydroxyethyl (meth) acrylate, (v) (poly) ethylene glycol (meth) acrylate having a degree of condensation of ethylene glycol of 1 to 100, Methoxy (poly) ethylene glycol (meth) acrylate, Lauroxy (poly) ethylene glycol (meth) acrylate; (Poly) propylene glycol (meth) acrylate having a degree of condensation of propylene glycol of 1 to 50; (Poly) alkylene such as 50 (poly) butylene glycol (meth) acrylate (alkylene group having 1 to 8 carbon atoms, alkylene group is linear or branched) (meth) acrylic acid ester having an oxide chain, ( vi) Glycerin (meth) acrylate (Meth) acrylic acid esters of polyhydric alcohols such as (vii) (meth) acrylic acid esters having an arylalkyl group such as benzyl (meth) acrylate, (viii) vinyl acetate, vinyl propionate, vinyl butyrate, hexane Vinyl esters having linear, branched or cyclic alkyl groups or alkenyl groups having 1 to 22 carbon atoms, such as vinyl acid, vinyl octoate, vinyl decanoate, vinyl laurate, vinyl palmitate, vinyl stearyl, etc. And (iii) (meth) acrylic acid ester having a C1-C22 hydrocarbon group is preferred.

  Among the monomers used in the present invention, monomers having only an amino group or its quaternary base and not having an ester group include (ix) dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, and dipropyl. (Meth) having amino groups such as aminopropyl (meth) acrylamide, diisopropylaminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, and di-t-butylaminopropyl (meth) acrylamide Acrylamides, (x) styrenes having amino groups such as dimethylaminostyrene, dimethylaminomethylstyrene, (xi) diallyl compounds having amino groups such as diallylmethylamine, diallylamine, etc. It is.

  In the method of the present invention, the above monomers (hereinafter referred to as “monomer (A)”) may be used alone or in admixture of two or more. Further, a monomer copolymerizable with the monomer (A) (hereinafter referred to as monomer (B)) may be copolymerized.

  Examples of the monomer (B) include vinyl alcohol; (meth) acrylamide having a hydroxyalkyl group having 1 to 22 carbon atoms such as hydroxypropyl (meth) acrylamide; acrylamide; diacetone (meth) acrylamide; N such as N-vinylpyrrolidone. -Vinyl cyclic amide; N- (meth) acryloylmorpholine; Vinyl chloride; Aconitrile; Vinyl compounds having a carboxyl group such as (meth) acrylic acid, maleic acid, itaconic acid, styrene carboxylic acid; 2-acrylamide-2- Examples thereof include vinyl compounds having a sulfonic acid group such as methylpropanesulfonic acid and styrenesulfonic acid.

  The content of the monomer (A) in the monomer component of the present invention is preferably from 10 to 100% by weight, more preferably from 20 to 100% by weight, based on the total amount of monomers, from the viewpoint of the odor reducing effect. Further, the content of the monomer (B) is preferably 0 to 90% by weight and more preferably 0 to 80% by weight with respect to the total amount of the monomer from the viewpoint of the odor reducing effect.

  When the polymer of the present invention is used for fiber modification, as the monomer component, the (i) (meth) acrylic acid ester having an amino group and (iii) a hydrocarbon group having 1 to 22 carbon atoms are used. It is preferable to use a mixture of (meth) acrylic acid ester, and the ratio of (i) and (iii) is such that (i) / (iii) (weight ratio) is in the range of 99/1 to 10/90. More preferred.

[Method for producing polymer]
The polymer production method of the present invention uses the above-mentioned hydroxy compound having a boiling point of 180 ° C. or more as a solvent, and polymerizes the monomer components as described above by the usual general solution polymerization method, suspension polymerization method or the like. However, radical polymerization is preferred.

  As the radical polymerization initiator used in the present invention, a general radical polymerization initiator can be used. For example, peroxide initiators such as lauroyl peroxide, benzoyl peroxide, ammonium persulfate; Examples thereof include azo initiators such as azobis (2,4-dimethylvaleronitrile) and 2,2′-azobisisobutyronitrile. The amount of the radical polymerization initiator used varies depending on the type and concentration of the monomer, the type of the polymerization initiator, the reaction temperature, etc., but is preferably 0.1 to 10 mol% with respect to the total amount of monomers, preferably 0.5 to 8 mol% is more preferable.

  Specifically as a manufacturing method of the polymer in this invention, the following manufacturing methods are mentioned.

  First, the reaction vessel is heated to a predetermined temperature. The temperature in the reaction vessel at that time can be freely set according to the type and amount of the radical polymerization initiator, the type of solvent, the type and concentration of the monomer, etc., but the half-life of the radical polymerization initiator is 200 minutes or less. Is preferable from the viewpoint of reaction control. Usually, the temperature is about 40 to 120 ° C, preferably 50 to 100 ° C. In addition, an appropriate amount of a solvent or a solvent and other components (monomer, etc.) may be added in advance to the reaction vessel. If necessary, oxygen in the reaction vessel may be distilled off by replacement with an inert gas such as nitrogen.

  Next, the monomer and the radical polymerization initiator are continuously or intermittently dropped into the reaction vessel. At this time, a monomer or a radical polymerization initiator may be dropped in a solvent. The concentration of the monomer and radical polymerization initiator at that time is preferably 20 to 100% by weight in the case of a normal monomer, and preferably 1 to 100% by weight in the case of a radical polymerization initiator. Moreover, each monomer, radical polymerization initiator, or a solution thereof may be dropped into the reaction vessel separately, or mixed and dropped. When dropping separately, the dropping timing and speed may be shifted. Each dropping may be performed continuously or intermittently. These dripping liquids may be used to distill away dissolved oxygen in the liquid by replacement with an inert gas such as nitrogen as required. The dropping time can be freely set according to the type and concentration of the monomer, the type and amount of the radical polymerization initiator, the type of solvent, the reaction temperature, etc., but the reaction rate of all monomers immediately after the completion of dropping of all monomers is 50 to 50%. 100% is preferable in terms of reaction control. The time is usually about 1 to 20 hours. Moreover, the temperature in the reaction container during dripping can be suitably changed within the said temperature range.

  In order to complete the polymerization reaction after completion of the dropping, it is preferable to hold the reaction solution within the above temperature range for a certain time. The holding time is about 0 to 15 hours.

[Polymer and its use]
In the method of the present invention, the polymer is obtained as a solution of a hydroxy compound having a boiling point of 180 ° C. or higher used as a solvent, but the solution can be used for applications such as fiber modification.

  The weight average molecular weight (Mw) of the polymer obtained by the method of the present invention is not particularly limited, but is preferably 2,000 or more, more preferably 3000 to 200,000 from the viewpoint of use as a fiber modifying polymer.

  In addition, Mw of the polymer of this invention uses the value by a gel permeation chromatography (GPC) measurement. As an eluent, any one of water, alcohol, chloroform, dimethylformamide, tetrahydrofuran, acetonitrile, and a combination of these solvents is used, and the molecular weight is converted to polyethylene glycol or polystyrene.

  According to the production method of the present invention, it is possible to obtain a polymer having an ester group and an amino group or a quaternary base thereof with a reduced odor by reducing the amount of odorous substances generated during or after the production of the polymer. . The polymer obtained in the present invention can be used for various applications, but is preferably used as a fiber-modifying polymer, and is particularly suitable as a polymer to be added to detergents and fiber treatment agents in which odor is a problem. It is.

  In the following examples, the weight average molecular weight of the polymer was measured according to the following method.

<Measurement of weight average molecular weight of polymer>
The weight average molecular weight (Mw) of the polymer was measured by GPC using Hitachi L-6000 type high performance liquid chromatography. The eluent flow pump is Hitachi L-6000, the detector is a Shodex RI SE-61 differential refractive index detector, the column is Asahi Pack's water gel filtration type GS-220HQ (exclusion limit molecular weight 3000) and GS-620HQ ( Exclusion limit molecular weight 2 million) was used in a double connection. The sample was adjusted to a concentration of 0.5 g / 100 ml with an eluent, and 20 μl was used. As the eluent, a 0.4 mol / L sodium chloride aqueous solution was used. The column temperature was 30 ° C. and the flow rate was 1.0 ml / min. Obtain a calibration curve using polyethylene glycol with molecular weights of 106, 194, 440, 600, 1470, 4100, 7100, 10300, 12600, 23000, etc. as the standard sample, and calculate the weight average molecular weight (Mw) of the polymer based on the calibration curve. Asked.

Example 1
A 1 L 4-neck separable flask equipped with a stirrer, a Dimroth reflux apparatus, and a thermometer was purged with nitrogen for a certain period of time. Thereto was added 73.3 g of triethylene glycol monophenyl ether (average number of moles of ethylene oxide added, 3 hereinafter), and the mixture was heated and held with stirring until the internal temperature reached 80 ° C.

  Separately, a monomer solution was prepared by uniformly mixing 213.6 g (1.36 mol) of dimethylaminoethyl methacrylate, 86.4 g (0.34 mol) of lauryl methacrylate, and 164.1 g of triethylene glycol monophenyl ether.

  Separately, an initiator in which 6.33 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (v-65B: manufactured by Wako Pure Chemical Industries, Ltd.) and 38.0 g of triethylene glycol monophenyl ether were uniformly mixed. A solution was made.

The monomer solution and the initiator solution were dropped into the above separable flask over 3 hours. Next, a solution prepared by dissolving 8.44 g of v-65B in 75.9 g of triethylene glycol monophenyl ether was added dropwise to the flask at a constant rate over 4 hours. After completion of dropping, the polymer was held at 80 ° C. for 2 hours to obtain 750 g of a polymer triethylene glycol monophenyl ether solution. The weight average molecular weight (Mw) of this polymer was 10,000. Further, the composition of this polymer analyzed by ¹ H-NMR was in accordance with the charged monomers.

Example 2
In Example 1, 750 g of a polymer triethylene glycol monophenyl ether was obtained in the same manner as in Example 1 except that the amount of v-65B in the initiator solution was changed to 4.22 g. Mw of the obtained polymer was 14000. Further, the composition of this polymer analyzed by ¹ H-NMR was in accordance with the charged monomers.

Example 3
In Example 1, 750 g of a polymer PhG solution was obtained in the same manner as in Example 1 except that ethylene glycol monophenyl ether (PhG: manufactured by Nippon Emulsifier Co., Ltd.) was used instead of triethylene glycol monophenyl ether. . Mw of the obtained polymer was 7000. Further, the composition of this polymer analyzed by ¹ H-NMR was in accordance with the charged monomers.

Comparative Example 1
In Example 1, 750 g of a polymer ethanol solution was obtained in the same manner as in Example 1 except that ethanol was used instead of triethylene glycol monophenyl ether. Mw of the obtained polymer was 5000. Further, the composition of this polymer analyzed by ¹ H-NMR was in accordance with the charged monomers.

Comparative Example 2
In Comparative Example 1, 750 g of a polymer ethanol solution was obtained in the same manner as in Comparative Example 1 except that the amount of v-65B in the initiator solution was changed to 4.22 g. Mw of the obtained polymer was 8800. Further, the composition of this polymer analyzed by ¹ H-NMR was in accordance with the charged monomers.

Comparative Example 3
After synthesizing in the same manner as in Comparative Example 2, 75 g of activated carbon (LH2C: manufactured by Nippon Environmental Chemicals) was added to 750 g of the polymer ethanol solution, and the mixture was stirred at room temperature for 12 hours. The solution was filtered with a membrane filter to obtain 600 g of a polymer ethanol solution. Mw of the obtained polymer was 8800. Further, the composition of this polymer analyzed by ¹ H-NMR was in accordance with the charged monomers.

Comparative Example 4
In Comparative Example 3, 580 g of a polymer ethanol solution was obtained in the same manner as in Comparative Example 3 except that the activated carbon was changed to S80 (Mitsubishi Chemical Calgon). Mw of the obtained polymer was 8800. Further, the composition of this polymer analyzed by ¹ H-NMR was in accordance with the charged monomers.

Comparative Example 5
In Comparative Example 3, 700 g of a polymer ethanol solution was obtained in the same manner as in Comparative Example 3 except that synthetic adsorbent KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) was used instead of activated carbon. Mw of the obtained polymer was 8800. Further, the composition of this polymer analyzed by ¹ H-NMR was in accordance with the charged monomers.

Comparative Example 6
The polymer was synthesized in the same manner as in Comparative Example 2 to obtain an ethanol solution of the polymer, and then vacuum dried at 50 ° C. for 1 hour to obtain 300 g of a polymer solid. The obtained polymer solid was dissolved in 450 g of ethanol to obtain 750 g of a polymer ethanol solution. Dimethylaminoethyl methacrylate and the like were present in the distilled ethanol solvent. Mw of the obtained polymer was 8800. Further, the composition of this polymer analyzed by ¹ H-NMR was in accordance with the charged monomers.

Comparative Example 7
In the same manner as in Comparative Example 6, 300 g of polymer solid was obtained. The obtained polymer solid was dissolved in 450 g of triethylene glycol monophenyl ether, and steam was fed into the solution at a rate of 7 (ml / h) under reduced pressure at 50 ° C. for 5 hours to obtain a triethylene glycol monophenyl ether solution of the polymer. It was.

  The monomer compositions, working solvents, post-treatment conditions, and weight average molecular weights (Mw) of the polymers obtained in Examples 1 to 3 and Comparative Examples 1 to 7 are summarized in Table 2. Moreover, the obtained polymer was added to the fiber treatment agent of the following composition, the odor was determined by the following criteria by five professional panelists, and the average value of the five persons is shown in Table 2.

<Fiber treatment agent composition>
Polymer 1.0% by weight
Amino-modified dimethylpolysiloxane (KF-864, manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0% by weight
Dialkyl (C12-14) dimethylammonium chloride 5.0% by weight
Alkyl (16-18 carbon atoms) trimethylammonium chloride 1.0% by weight
Polyethylene glycol (EO40) alkyl (C12-14) ether 9.0% by weight
Ethanol 1.0% by weight
Glycerin 2.0% by weight
Triethylene glycol monophenyl ether 4.0% by weight
Hydrochloric acid pH 4.0 (20 ° C) Water balance <Odor criteria>
0 ... Does not smell 1 ... Small smell 2 ... Smell 3 ... Smell strengthens

Claims (5)

  A method for producing a polymer having an ester group and an amino group or a quaternary base thereof in a molecule, wherein a hydroxy compound having a boiling point of 180 ° C. or higher is used as a solvent, and a monomer having an ester group and an amino group or a quaternary base thereof A method for producing a polymer comprising polymerizing a monomer component containing a monomer having a monomer (provided that a monomer having an ester group and a monomer having an amino group or a quaternary base thereof may be the same monomer).   The hydroxy compound having a boiling point of 180 ° C. or more is selected from alkylene glycol having 2 to 3 carbon atoms of alkylene group or monoalkyl (alkyl group having 1 to 12 carbon atoms) or aryl ether of polyalkylene glycol, and 2 to 4 valent polyol. The method for producing a polymer according to claim 1, wherein the polymer is at least one kind.   The method for producing a polymer according to claim 1 or 2, wherein the hydroxy compound having a boiling point of 180 ° C or higher is a monophenyl ether of ethylene glycol or polyethylene glycol.   The polymer component according to any one of claims 1 to 3, wherein the monomer component contains an acrylic ester or methacrylic ester having an amino group, and an acrylic ester or methacrylic ester having a hydrocarbon group having 1 to 22 carbon atoms. Production method.   The polymer for fiber modification obtained by the manufacturing method in any one of Claims 1-4.