JPS6213417A - Modifier and modification - Google Patents

Abstract

PURPOSE:A modifier for polymerizing an ethylenically unsaturated monomer, which can give a polymer excellent in dyeability and antistatic property and a low-foaming polymer emulsion excellent in mechanical and chemical stability, comprising a specified sulfonic acid (salt). CONSTITUTION:A modifier for polymers, comprising a sulfonic acid (salt) of formula I [wherein R is H or CH3, A1-2 are each a 2-4C (substituted) alkylene, a and b are each 1 or larger, X1-2 are each H or a group of formula II (wherein m, the valence of the cation, is 1-2), Y is H or acyl, and Z is a 1-5C (F- substituted) alkylene or SO2] is obtained by introducing a sulfonic acid (salt) group into each aromatic ring of a bisphenol by using a sulfonating agent such as chlorosulfuric acid, further reacting the product with glycidyl (meth)acrylate and, if required, converting it into a salt by neutralization with an alkali (alkaline earth) metal hydroxide. An ethylenically unsaturated monomer is polymerized in the presence of a polymerization initiator, etc., by adding said modifier in an amount of 0.2-5wt% (for the production of a hydrophobic polymer) or 2-80wt% (for the production of a hydrophilic polymer).

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a modifier and a modification method.

[Prior art:] Conventionally, polymers such as (meth)acrylonitrile (abbreviated as acrylonitrile and/or methacrylonitrile. The same expressions will be used hereinafter), (meth)acrylic acid or a salt or ester thereof, vinyl chloride, It is known to use a sulfonated ester of phenol or its alkylene oxide adduct and (meth)acrylic acid as a modifier for polymers of ethylenically unsaturated monomers such as vinylidene chloride and styrene.

[Problem that the invention seeks to solve]

The polymer obtained by this method has the problem that the polymerization rate of the monomer does not increase; the performance such as the dyeability of the polymer and the properties of the emulsion and the film obtained from the emulsion are not necessarily satisfactory. be.

[Means for solving problems]

The present inventors have developed a modifier for polymers and a method for modifying polymers that increase the polymerization rate of monomers and improve performance such as dyeability of the polymer and the characteristics of emulsions and films obtained from the emulsions. As a result of extensive research, we have arrived at the present invention.

The present invention is based on the general formula (wherein R is a hydrogen atom or a methyl group.A1・A
2 is an alkylene group having 2 to 4 carbon atoms or an alkylene group having a substituent. a and b are integers of 1 or more. X
, , X2 are hydrogen atoms or SO3M''J1 (, and at least one of x, , x2 is an 80.M'' group.

m is an integer of 1 to 2 and represents the valence of the cation M. Y is a hydrogen atom or an/I/ group. 2 is an alkylene group having 1 to 5 carbon atoms, a fluorine-substituted alkylene group having 1 to 5 carbon atoms, or SO2. ) Sulfonic acid (
A modifier for polymers (first invention) characterized in that it consists of a salt); and a method of modifying using an anionic Ti monomer during the production of a polymer of an ethylenically unsaturated monomer. A method for modifying a polymer (second invention) characterized in that a sulfonic acid (salt) represented by the general formula (1) is used as an anionic monomer.

In the present invention, modifiers include not only those used for the purpose of modifying the polymer, but also those used for other purposes (for example, as an emulsifier for heavy emulsification), resulting in the modification of the polymer. Also included are those that are

In general formula (1), A1. Examples of the alkylene group having 2 to 4 carbon atoms in A2 include ethylene group, propylene J, (,
) -IF Ren group, etc., alkylene groups having 'lt,' substituents include phenylethylene group, phenylmethylethylene group, hydroxypropylene group, and the like. Among these, preferable ones have 2 to 4 carbon atoms.
is an alkylene group, and a particularly preferable one is carbon@2
or 3 alkylene group. These alkylene groups form an oxyalkylene group together with an oxygen atom;
But that's fine. Preferred are polymer chains of 1 oxyethylene group, oxypropylene group, or a combined group (block or random) of 1-oxyethylene group and oxypropylene group.

a and b are integers of 1 or more, preferably 2-30, particularly preferably 3-15. When a+b is 0, the compatibility with the monomer to be polymerized is poor and it is difficult to form a copolymer. The sum of a and b is usually 2 to 40, preferably 6 to 3
It is 0.

The acyl group of Y is a linear or branched unsaturated fatty acid having 1 to 24 carbon atoms [(meth)acrylic acid, (iso)
[crotonic acid, oleic acid, etc.] and saturated fatty acids [acetic acid, stearic acid, etc.] are hydrogen atoms or methyl groups. ].

Monovalent or divalent cations of M include hydrogen, alkali metals (sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.) ammonium,
Examples include organic amine cations (alkanolamine cations, lower alkylamine cations, etc.). Preferred among these are alkali metals (especially sodium and potassium) and ammonium.

The alkylene group having 1 to 5 carbon atoms of Z is -CI-12
−.

C113C, II, CF.

? 113 Specific examples of the nulfonic acid (salt) represented by the general formula (1) include the compounds shown in Table 1. Table-(1)0)
, represents the addition of 5 moles of PO, and (PO)s (EO)to represents the block addition of 5 moles of PO and 8010 moles of PO to bisphenols in this order.
15) shows the random addition of a mixture of 5 moles of Eo and 5 moles of PO to bisphenols, and the same description will be used below.

For example, the nulfonic acid (salt) represented by the general formula (1) is (
1) Binuphenols [bispheno-)VA,
F+ 2+27-Binu(hydroxypheni)V)butane, 2,2'-bis(hydroxypheni/L/)hexafluoropropane, bispheno-/L, 'S, etc.], with a nulphonating agent ( After adding a sulfonic acid (salt) group using fuming sulfuric acid, sulfuric anhydride, sulfuric acid, chlorosulfuric acid, etc.), react with glycidyl ether (meth)acrylate to make a salt if necessary (as a method for making a salt) method of neutralizing with alkali metal or alkaline earth metal hydroxide, aqueous ammonia, organic amine, etc.) After esterifying the ester, a sulfonic acid (salt) group is added using a sulfonating agent, and if necessary, a method similar to that described above is used to convert the sulfonic acid (salt) group into a salt.

As the polymer to be modified using the modifier of the present invention, polymers used as synthetic fibers, synthetic resins, synthetic rubbers, synthetic resin emulsions, and synthetic rubber latexes can be used. Examples include polymers of ethylenically unsaturated monomers such as: (a) Monomers containing nitrile groups: (meth)acrylonitrile, etc. (+)) Unsaturated carboxylic acids [(meth)acrylic acid, maleic acid, etc. esters of acids, fumaric acid, itaconic acid, etc.
: Alkyl group having 1 to 20 carbon atoms (methyl, ethyl.

(butyl, 2-ethylhexy) V group, etc.)
Glycol (ethylene glycol) v + 1
+4-butanedio-/L/.

(C) Amides of unsaturated carboxylic acids such as (meth)acrylamide (di-halogen-containing monomers; chloride); di(meth)acrylates such as polypropylene glycol; hinyl, vinylidene chloride, chlorobrene, etc. fc) Aromatic vinyl monomer. T° form: styrene, α-memethynuthylene, chlorostyrene, vinyl 1-toluene, etc. (f) Aliphatic hydrocarbon monomer: ethylene, propylene, butadiene, isoprene, etc. (g) Vinyl ether or (meth)allyl ester: Vinyl acetate , vinyl propionate, dipini/lefthale
1. Allyl acetate, diallyl phthalate, etc. (h) Unsaturated^rocarboxylic acid or its salt: (meth)acrylic acid, maleic acid, fumaric acid.

ichconic acid, etc. and their salts, etc.

i7'i. Specific examples of merging include polymerized resins described on pages 7 and 113 to 217 of ``Basic Synthetic Resin Chemistry'' (written by Tadahiro Miba, published by Gihodo on November 25, 1975). It will be done.

+The amount of the modifier of the invention can be varied depending on the type of polymer, monomer composition, purpose, water retention performance, etc. When producing a hydrophobic polymer for the purpose of dyeability, antistatic property, etc., the modifier of the present invention is usually added in the polymer in an amount of 0.1 to 10 g, preferably 0.2 to 10 g, on a weight basis.
It is recommended that the content be 5%. If the amount exceeds 10, the affinity for water becomes too large, which is often disadvantageous. On the other hand, when producing a hydrophilic polymer (for example, a water-soluble resin), the modifier of the present invention is added to the polymer in an amount of usually 2 to 80 parts, preferably 10 to 60 parts by weight. It is better to

Modification of a polymer with the modifier of the present invention can be carried out in various ways.

The polymerization method may be any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.

When carrying out polymerization using the modifier of the present invention, the polymerization may be carried out by mixing it into the monomer (mixture), or partially polymerized,
It may be mixed into a monomer-polymer mixture or polymer to perform graft or block polymerization. Also, polymer molded products (
It can also be polymerized on the surface of fibers, textile products, etc.), films, or cast products.

The modifier of the present invention is particularly useful as a polymerizable emulsifier used in emulsion polymerization of monomers. Such use as an emulsifier can be achieved in various ways. For example, in the emulsification method using a conventional emulsifier, the modifier of the present invention can be used in place of the conventional emulsifier.

In addition, the modifier of the present invention or 4 to be polymerized with it
F. , :, After pre-polymerizing the H-form, the monomer to be polymerized or the monomer to be polymerized (11
Polymerization can also be carried out by adding the isomer and the modifier of the present invention to the polymerization system.

1. In the various polymerization methods described above, the polymerization can be initiated by irradiation with electron beams, gamma rays or ultraviolet rays, by heating, and by using initiation n]. Examples of initiators include persulfates (such as ammonium persulfate); peroxy compounds (benzoyl peroxide, lauroyl peroxide, hydrogen peroxide, etc.); azo initiators (azobisisobutyronitrile, etc.), and niredox initiators. Initiators such as (sulfites and) oxy-compounds, hydrogen peroxide and Fe2+ salts, etc.) can be used.

In the above various polymerization methods, during polymerization, the medium [solvents commonly used in solution polymerization; dimethylformamide, dimethylacetamide, dimethylnulphoxide, concentrated zinc chloride aqueous solution, etc.; commonly used in emulsion polymerization and suspension polymerization; Aqueous media used: water, mixed solvents of water and water-soluble organic solvents (methanol, isopropanol, acetone, etc.)].

Polymerization regulators [such as chain transfer agents such as various mercaptans (eg dodecyl mercaptan)].

A dispersant (such as partially saponified polyvinyl alcohol) can be used if necessary. In addition, in the case of emulsion polymerization, a normal emulsifier [7=one activator (
'l' f Sodium sylbenzene sulfonate, sodium lauryl sulfate, sodium alkyl diphenyl ether dinulfonate, polyoxyethylene alkyl ether/ammonium sulfate, etc.) and/
Or non-ionic active agent (polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether).

Polypropylene glyco-l-ethylene oxide adduct, etc.) can also be used in combination, but it is not preferable to use a large amount because it goes against the purpose of the present invention.

In the above various polymerization methods, the polymerization temperature is determined by the polymerization method,
The temperature is usually -5 to 150°C, although it varies depending on the type of body to be copolymerized.

In addition to the modifier of the present invention, Japanese Patent Application No. 59-27715 and Japanese Patent Application No. 59-198 are used in the various polymerization methods described in "-". 8894
No. 5, Japanese Patent Application No. 1983-38946, and Japanese Patent Application No. 1983-
Modifiers described in each specification of No. 52896 can be used in combination. The weight ratio when used in combination can vary within a wide range, for example from 1 (invention):9 to 9:1.

Still other anionic monomers [sulfopropy/I/(Me,
1 Pa″'yl)v-5,,z”V 72 /l/″′
1゛“← Nurpponated product of ester of alcohol or its alkylene oxide adduct and (meth)acrylic acid, etc.] can also be used in combination. When used in combination, the modifier of the present invention and other anionic monomers The amount of the modifier of the present invention is usually 30% or more, preferably 50% based on the total weight of
Make it so that it becomes more than that.

〔Example〕

The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

Example 1 Compound N[11 in Table 1 was used as a modifier of the present invention, and was used to modify a polymer.

Acrylonitrile 20g, Methyl acrylate/L/l g
.

Compound N[11 in Table-1 is 0.4, 9. Azobisisobutyronitrile 0.82 fl + oxalic acid 0.1. ! ;
! , ethylenediamine 70.05 g, titanium oxide 00
8 g of dimethyl sulfoxide and 79 g of dimethyl sulfoxide.
After polymerizing at 2°C for 10 hours, the polymerization temperature was increased to 50°C.
The temperature was raised to 1, and polymerization was continued for an additional 15 hours. The polymerization rate was 99, and the [η] of the polymer was 1.67.

After collecting unreacted monomers, this polymer solution was used as a spinning stock solution and was spun in an aqueous solution of 30% dimethyl sulfoxide at 30°C. The obtained undrawn yarn was drawn 5 times in an aqueous solution (temperature 95°C) of 6 ml of dimethyl sulfoxide.

This drawn yarn was washed with water, dried, and heat treated to obtain a glossy white fiber without devitrification. Basic dye PASIC BLUE GO
When dyeing was carried out at 98°C for 1 hour at a bath ratio of 1:100, the dye absorption rate was 98%.

Example 2 Compound NCt2 shown in Table 1 was used as a modifier of the present invention to modify a polymer.

Under nitrogen atmosphere, methyl methacrylate) 50.9゜Table-
2 g of compound N112 of No. 1 and 0.1.9 g of lauroyl peroxide were placed in a galanum mold, and polymerization was carried out at 60"C for 4 hours to obtain a polymer plate with a thickness of 2 mm. After cooling, it was taken out from the mold. The polymer has a polymerization rate of 99.7
%, it was a glassy resin with good transparency. When the surface resistivity of this resin plate was measured according to the method of JIS K6911-1979, it was 6×10 11 Ω, indicating good antistatic properties.

Example 3 Compound Nn 5 shown in Table 1 was used as a modifier of the present invention to modify a polymer.

117.5 g of ion-exchanged water was placed in a reaction vessel equipped with a stirrer, 2 dropping funnels, a nitrogen inlet, a thermometer, and a reflux condenser.
The compound Nn5 in Table 1 was 1.6.9 g, sodium hydrogen carbonate 0.08 g, and ammonium persulfate 0.16.9 g. Styrene 22I and 18 g of butyl acrylate were charged and emulsified with stirring, and after nitrogen substitution, polymerization was carried out at 75° C. for 30 minutes with stirring. Continued ion exchange water 134.57. Table-1
Compound 5 is s, s, 9 is hydrogen carbonate) IJium 0
．． 28.5+.

Ammonium persulfate 0.56 ji, styrene 77g
An emulsion containing 68 g of butyl acrylate was added dropwise from the dropping funnel over 2 hours, and polymerization was carried out at 80°C with stirring.
! After adding 7, the temperature was raised to 85°C and polymerization was carried out for 2 hours.

Table 2 shows the results of the monomer polymerization conversion rate; the amount of coagulum produced; the mechanical stability, chemical stability, and foaming properties of the emulsion; and the water resistance and adhesiveness of the film.

Comparative Example 1 In Example 3, the same ITc 41 (Nosu 1゛ium sulfobrobyl methacrylate-1. A large amount of coagulum was generated and the emulsion could not be made.

Comparative Example 2 In Example 3, sodium todenlebenzene sulfonate from the same city was used instead of compound Nn5 in Table 1, and polymerization was carried out according to the method of Example 3 to obtain an emulsion. Performance test results such as monomer polymerization conversion rate are shown in Table 2.

Table-2 (Note-1) 1.5 g of Zimmer polymerization conversion rate polymer emulsion was heated to 1.5 at 130°C.
The weight of the evaporated residue after drying for a period of time was measured and calculated as a percentage of the theoretical solid content weight at 100% polymerization.

(Note-2) The coagulum was filtered through a wire mesh with a mesh size of 150, and the filtration residue was washed with water and dried at 130°C for 5 hours to obtain a coagulum. The dry weight was converted into the monomer used by adding 1°.

(Note-3) Mechanical stability of the emulsion Take 200g of the polymer emulsion in a beaker and use a homomixer for 10.
000 rpm for 30 minutes, the resulting coagulate was stirred at 150 rpm
They were separated from each other using mesh wire mesh, washed with cold water, and dried at 130°C for 5 hours. The weight of the dry matter was calculated based on the weight of solids in the collected emulsion.

(Note-4) Chemical stability of emulsion Solid content 0.5%
The volume of '10CaCI2 required to coagulate and separate 50 ml of a polymer emulsion diluted with water (m
It was a hailstorm.

(tE-5) Polymer emulsion 30% diluted with water to 3% foamable solid content of emulsion
100 mg of me was placed in a cylinder with a stopper, shaken vigorously once, and after 5 minutes was washed with foam ri' (ml).

(Note-6) Spread the water-resistant ITC combined emulsion of the film on the Nuride Galanu,
It was dried at 0''C for 8 hours and then at 20C for 24 hours to produce a 0.2mm thick -q c+ film.

The water resistance of this film was tested using the ILS K-6828 water drop test method.

(?fE-7) Film Adhesion Method A cellophane adhesive tape was attached to the film prepared by the method described in Note 6, and the adhesive strength between the film and the cellophane adhesive tape was measured by a 180' peel test at 20°C.

(Note-1 COT in emulsion waste liquid) The polymer emulsion was freeze-broken by freezing at -10°C for 24 hours, and after melting at 30°C, the polymer was distributed from house to house. CC of P liquid]r
) was measured according to JIS K 0102-1971.

〔Effect of the invention〕

The modifier of the present invention has a higher polymerization rate of monomers than known modifiers made of anionic monomers; improved performance (degree of polymerization, dyeability, antistatic property, etc.). Polymers are obtained; the polymer emulsions obtained have good mechanical and chemical stability and low foaming; the films and materials obtained from the polymer emulsions have excellent water resistance. and has adhesive properties.

In addition to the above effects, the modifier of the present invention does not devitrify; it imparts hydrophilicity; it prevents dirt such as lint oil, grime, etc. from adhering to it, and even if it does, it can be easily removed. When extracting a polymer from an emulsion, it is possible to obtain a polymer with properties such as:
It also has the effect of providing a polymer emulsion with properties such as almost no emulsifier flowing out into wastewater.

Polymers modified by the method of the present invention are useful as synthetic fibers, synthetic resins for fiber processing, paper processing agents, hair spray resins, and the like.

Claims (1)

[Claims] 1. General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R is a hydrogen atom or a methyl group. A_1,
A_2 is an alkylene group having 2 to 4 carbon atoms or an alkylene group having a substituent. a and b are integers of 1 or more. X_1 and X_2 are hydrogen atoms or SO_3M^1^/
^m group, and at least one of X_1 and X_2 is SO
_3M^1^/^m group. m is an integer of 1 to 2 and represents the valence of the cation M. Y is a hydrogen atom or an acyl group. Z is an alkylene group having 1 to 5 carbon atoms, a fluorine-substituted alkylene group having 1 to 5 carbon atoms, or SO_2. ) A modifier for polymers comprising a sulfonic acid (salt) represented by: 2. The modifier according to claim 1, wherein Z is ▲a numerical formula, a chemical formula, a table, etc.▼. 3. The acyl group has ▲ mathematical formulas, chemical formulas, tables, etc. ▼ group (
In the formula, R is a hydrogen atom or a methyl group. ) The modifier according to claim 1 or 2, which is 4. In the method of modifying using anionic monomers during the production of polymers of ethylenically unsaturated monomers, there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. as anionic monomers ▼ (I) (wherein R is a hydrogen atom or a methyl group. A_1,
A_2 is an alkylene group having 2 to 4 carbon atoms or an alkylene group having a substituent. a and b are integers of 1 or more. X_1 and X_2 are hydrogen atoms or SO_3M^1^/
^m group, and at least one of X_1 and X_2 is SO
_3M^1^/^m group. m is an integer of 1 to 2 and represents the valence of the cation M. Y is a hydrogen atom or an acyl group. Z is an alkylene group having 1 to 5 carbon atoms, a fluorine-substituted alkylene group having 1 to 5 carbon atoms, or SO_2. ) A method for modifying a polymer, which comprises using a polymer modifier consisting of a sulfonic acid (salt). 5. The method according to claim 4, wherein Z is ▲a mathematical formula, a chemical formula, a table, etc.▼. 6. The acyl group has ▲ mathematical formulas, chemical formulas, tables, etc. ▼ group (
In the formula, R is a hydrogen atom or a methyl group. ) The method according to claim 4 or 5. 7. The sulfonic acid (salt) is 0.0% based on the total weight of monomers.
7. A method according to any one of claims 4 to 6, using from 1 to 80%. 8. The method according to any one of claims 4 to 7, wherein the ethylenically unsaturated monomer is emulsion polymerized in the presence of the sulfonic acid (salt).