JPS6383109A - Modifier for polymer and modification method - Google Patents

Abstract

PURPOSE:To obtain the title modifier which is excellent in compatibility with an ethylenically unsaturated monomer and can give a uniform copolymer, comprising a sulfonic acid (salt) of a specified formula. CONSTITUTION:A modifier for polymer, comprising a sulfonic acid (salt) of formula I (wherein R is H or CH3, X is a group of formula II or III, A is a 2-4C alkylene, n and l are each an integer >=2, M is a monovalent or bivalent cation and m is 1 or 2), e.g., a compound obtained by esterifying (meth)acrylic acid with a polyoxyalkylenealkyl halide and converting the product into a sulfonic acid (optionally, salt) by treatment with a sulfonating agent. This modifier has good compatibility with the monomer to be polymerized, so that it can give a uniform polymer. Further, a polymer of improved performances (degree of polymerization, dyeability, antistatic property, etc.) can be obtained with a monomer conversion at least equivalent to that attained when a modifier comprising a well-known anionic monomer is used. The obtained polymer emulsion has excellent mechanical and chemical stability and a reduced foaming property, and a film or a coating obtained therefrom is excellent in water resistance and adhesiveness.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polymer modifier and a modification method.

[Conventional technology]

Conventionally, polymers such as (meth)acrylonitrile (abbreviated as acrylonitrile and/or methacrylonitrile) are used.

Similar expressions will be used below. ), (meth)acrylic acid or its salts or esters, vinyl chloride, vinylidene chloride, styrene, and other ethylenically unsaturated monomers (hereinafter referred to as monomers). ) It is known to use acrylate (salt).

[Problem that the invention seeks to solve]

However, sulfoalkyl (meth)acrylates (
salt) has poor compatibility with the monomer to be polymerized, making it impossible to obtain a uniform copolymer.

[Means for solving problems]

The present inventors have conducted intensive studies on polymer modifiers and polymer modification methods that have good compatibility with the monomers to be polymerized and can yield uniform copolymers. We have arrived at the present invention. That is, the present invention is an alkylene group represented by general formula ~4. n is an integer of 2 or more. l is an integer of 2 or more. M is a monovalent or divalent cation. m is an integer of 1 to 2, and represents the valence of the cation M. ) A polymer modifier (first invention) consisting of a sulfonic acid (salt) represented by A method for modifying a polymer (second invention) characterized in that the method uses a sulfonic acid (salt) represented by the general formula (1) 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 emulsion polymerization) and resulting in modification of the polymer. Also included are those that are

In general formula (1), examples of the alkylene group having 2 to 4 carbon atoms in A include an ethylene group, a propylene group, and a butylene group. These alkylene groups together with oxygen form oxyalkylene groups, and the oxyalkylene groups may be intercalated or different (block or random).

Preferred are oxypropylene groups and combination groups (block, random) of oxyethylene groups and oxypropylene groups, and particularly preferred are oxypropylene groups in which the number of oxypropylene groups in n oxyalkylene ÷ AO + groups is 2 or more. It is.

n is an integer of 2 or more, preferably 2-80, particularly preferably 8-15. When n is 1 or less, the compatibility with the monomer to be polymerized is poor, making it difficult to form a copolymer.

j is an integer of 2 or more, preferably 2-80, particularly preferably 2-5.

Monovalent or divalent cations of 81 include hydrogen, alkali metals (sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.), ammonium, organic amine cations (alkanolamines, lower alkylamines, etc.) ) can be given. Preferred among these are alkali metals (especially sodium and potassium) and ammonium.

As a specific example of the compound represented by the general formula (1), Table-
I can give you one thing.

In the following, EO is ethylene oxide and PO is propylene oxide (PO). (EO)%01omol, E0
A block adduct in which 5 moles were added in this order, (PO/E
O) (5/8) indicates a random adduct obtained by adding a mixture of 5 moles of P0 and 8 moles of EO, and the same description will be used below.

Table 1 (1) Method of esterifying polyoxyalkylene alkyl halide and (meth)acrylic acid and then converting the polyoxyalkylene alkyl halide and (meth)acrylic acid into sulfonic acid and, if necessary, a salt using a sulfonating agent. (I) Hydroxyalkylsulfonic acid (l and (meth) ) A method of etherifying acrylic acid with an alkylene oxide adduct and making a salt if necessary; (2) A method of esterifying polyoxyalkylenealkylsulfonic acid (shame) and (meth)acrylic acid and making a salt if necessary. In addition, in the case of X = -CH, -, for example, ~) a method of etherifying polyoxyalkylene alkyl halide and (meth)allylic alcohol and then converting the polyoxyalkylene alkyl halide and (meth)allylic alcohol into a sulfonic acid and optionally a salt using a sulfonating agent; (V) Hydroxyalkylsulfonic acid (method of etherifying a button and an alkylene oxide adduct of (meth)allyl alcohol and converting it into a salt if necessary, (b) Polyoxyalkylenealkylsulfonic acid (m), !-(meth) Examples include a method of etherifying allyl alcohol and, if necessary, converting it into a salt.

In addition, as a sulfonating agent, sulfite or sulfite@C
sodium sulfite, potassium sulfite, etc.). Further, examples of the method for making a salt include a method of neutralizing an alkali metal or alkaline earth metal hydroxide with aqueous ammonia, an organic amine, or the like. If sulfite is used as the sulfonating agent, no further manipulation is required since it forms a salt.

As the polymer to be modified using the modifier of the present invention, polymers used as synthetic am, synthetic resin, synthetic rubber, synthetic resin emulsion, and synthetic rubber latex can be used. Examples include polymers of ethylenically unsaturated monomers such as the following: (a) Monomers containing nitrile groups: (meth)acrylonitrile, etc. (b) Unsaturated carboxylic acids [(meth)acrylic acid, maleic acid, etc. , fumaric acid, itaconic acid, etc.]: alkyl (meth)acrylates having an alkyl group having 1 to 20 carbon atoms (methyl, ethyl, butyl, 2-ethylhexyl group, etc.); glycols (ethylene glycol, 1
．． 4-butanediol, polypropylene glycol, etc.) mono- or di(meth)acrylates; maleic acid,
Diesters or half-esters of fumaric acid or itaconic acid, etc. (C) Amides of unsaturated carboxylic acids: (meth)acrylamide, etc. (d) Halogen-containing monomers: vinyl chloride, vinylidene chloride, chlorobrene, etc. (e) Aromatic vinyl Monomer: Styrene, α-methylstyrene, chlorostyrene, vinyltoluene, etc. (f) Aliphatic hydrocarbon monomer: Ethylene, propylene, butadiene, isoprene, etc. (g) Vinyl ester or (meth)allyl ester:
Vinyl acetate, vinyl propionate, divinyl phthalate, allyl acetate, diallyl phthalate, etc. (h) Unsaturated carboxylic acids or salts thereof: (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, etc., and salts thereof.

A specific example of the polymer is "Basic Synthetic Resin Chemistry" mold resin.

The amount of the modifier used in the present invention can be varied depending on the type of polymer, monomer composition, purpose, required performance, etc. When producing a hydrophobic polymer for the purpose of dyeability, antistatic property, etc., the modifier of the present invention is usually 0.1 to 20%, preferably 0.2%, based on the weight of the polymer.
It is recommended that the content be 10%. If it exceeds 20%, 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 contained in the polymer in an amount of usually 2 to 80% by weight, preferably 10 to 60%.
It is better to set it to 6.

Modification of polymers with the modifier of the present invention can be carried out in a step-by-step manner.

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 polymer (mixture).
It may be mixed into a monomer-polymer mixture or polymer to perform graft or block polymerization. Also, polymer molded products (
Polymerization can also be carried out on surfaces such as fibers, textile products, etc.), films or cast articles.

The modifier of the present invention is particularly useful as a polymerizable emulsifier used in emulsion polymerization of monomers. Such use as emulsifier can be carried out in a discrete manner. For example, in an emulsion polymerization method using a conventional emulsifier, the modifier of the present invention can be used in place of the conventional emulsifier.

Furthermore, after the modifier of the present invention or the monomer to be polymerized with the modifier is prepolymerized, the modifier of the present invention is further polymerized with the monomer to be polymerized or the monomer to be polymerized. Polymerization can also be carried out by adding it to the polymerization system.

In the various polymerization methods described above, polymerization can be initiated by irradiation with electron beams, gamma rays, or ultraviolet rays, by heating, and by using an initiator. In the method using an initiator,
Persulfates (such as ammonium persulfate) as initiators;
Peroxy compounds (benzoyl peroxide, lauroyl peroxide, hydrogen peroxide, etc.); Azo initiators (azobisisobutyronitrile, etc.); Redox initiators (sulfites and peroxy compounds, hydrogen peroxide and Fe2+)
Initiators such as salts, etc.) can be used.

In the above various polymerization methods, during polymerization, the medium [solvent commonly used in solution polymerization; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, concentrated aqueous zinc chloride solution, etc.; commonly used in emulsion polymerization and suspension polymerization; Aqueous media: water, mixed solvents of water and water-soluble organic solvents (methanol, isopropanol, acetone, etc.)], polymerization regulators (chain transfer agents such as various mercaptans (e.g. dodecyl mercaptan), etc.), dispersion An agent (partially saponified polyvinyl alcohol, etc.) can be used if necessary. In addition, in the case of emulsion polymerization, ordinary emulsifiers that do not have copolymerizability [anion activators (sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyl ether disulfonate, ammonium polyoxyethylene alkyl ether sulfate, etc.) are used. and/or a nonionic activator (holoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polypropylene glycol ethylene oxide adduct, etc.)] may be used in combination, but their use in large amounts is contrary to the purpose of the present invention. Undesirable.

In the above various polymerization methods, the polymerization temperature is determined by the polymerization method,
It varies depending on the type of monomer to be copolymerized, but
It is usually -5 to 150°C.

In the above-mentioned polymerization method, in addition to the modifier of the present invention, other anionic monomers [sulfopropyl (meth)acrylate, styrene sulfonate, alcohol having an aromatic nucleus or its alkylene oxide adduct] and (meta)
A sulfonated product of ester with acrylic acid, etc.] can also be used in combination. When used together, the amount of the modifier of the present invention is usually 80% or more, preferably 5096 or more, based on the total weight of the modifier of the present invention and other anionic monomers.

〔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 The sulfonic acid (a No. 1) shown in Table 1 was used as the modifier of the present invention, and was used to modify a polymer.

Acrylonitrile 20f1 Methyl acrylate IF.

Sulfonic acids in Table 1 (ωNo, l is 0.49, azobisisobutyronitrile 0.821, oxalic acid o, 1y, ethylenediamine O, OIM, titanium oxide o, o 8
A mixture of F and dimethyl sulfoxide 79F was heated at 42°C.
After polymerization for 10 hours, the polymerization temperature was raised to 50° C. and polymerization was continued for an additional 15 hours. The obtained polymer was a homogeneous copolymer with a polymerization rate of 99.2% and a ■ value of 1.68.

After collecting unreacted monomers, this copolymer solution was used as a spinning stock solution and was spun in an aqueous solution of 30% 80'O dimethyl sulfoxide. The obtained undrawn yarn was drawn five times in an aqueous solution containing 6% dimethyl sulfoxide (temperature: 95° C.). This drawn yarn was washed with water, dried, and heat treated to obtain glossy white fine fibers without devitrification. Basic dye PASIC BLUE G
O was used at 896% of the fiber weight, and the bath ratio was 1:100.
When dyed at 8° C. for 1 hour, the dye absorption rate was 98%.

Example 2 The sulfonic acid (a No. 8 in Table 1) was used as the modifier of the present invention to modify a polymer.

Under nitrogen atmosphere, methyl methacrylate 50jF, Table-
1 sulfonic acid (fID No. 8 to 29.) and lauroyl peroxide o, i F were placed in a glass mold and polymerized at 60°C for 4 hours to obtain a polymer plate with a thickness of 2. After cooling, the mold The polymer taken out was a glass-like resin with a polymerization rate of 99.94 and uniform transparency.The surface resistivity of this resin plate was determined according to JISK-6911.
-4 x 10" as measured by the method of 1979
Ω, and the band m prevention property was good.

Example 8 The sulfonic acid (m No., 5) in Table 1 was modified to
This was used as a ll agent to modify the polymer.

Ion-exchanged water 117.5F was placed in a reaction vessel equipped with a stirrer, dropping funnel, nitrogen inlet, thermometer, and reflux condenser.
Sulfonic acid (salt) No. 5 in Table 1 was added to 1.6 F sodium bicarbonate 0.08 f, ammonium persulfate 0.
16F, styrene 2211, and butyl acrylate) 18F 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 1
84.5 j', sulfonic acid (fat) No. in Table-1
, 5 to 5.6N.

Sodium bicarbonate 0.28, ammonium persulfate 0
．． 56f, styrene 77f and butyl acrylate 6
An emulsion consisting of 89 was added dropwise from a dropping funnel over 2 hours, and polymerization was carried out at 80°C with stirring. After adding 18f of ammonium persulfate 1y6 aqueous solution, the temperature was raised to 86°C.
Polymerization was carried out for a period of time to obtain a uniform emulsion. Table 2 shows the test results for the monomer polymerization conversion rate, the amount of coagulum produced, the mechanical stability and chemical stability of the emulsion, and the water resistance and adhesion of the foamable film.

Comparative Example 1 In Example 8, the same weight of sodium sulfopropyl methacrylate was used in place of compound NO, 5 in Table 1, and polymerization was carried out according to the method of Example 8, but a large amount of coagulum was produced No emulsion was obtained.

Comparative Example 2 In Example 8, the same weight of sodium dodecylbenzenesulfonate was used in place of Compound No. 5 in Table 1, and polymerization was carried out according to the method of Example 8 to obtain an emulsion. Performance test results such as monomer polymerization conversion rate are shown in Table 2.

Table-2 (Note-1) Monomer polymerization conversion rate: Take a polymer emulsion of 1.51 and convert it to 180'0.
After drying for 5 hours, the weight of the evaporation residue was measured and expressed as a percentage of the theoretical solid content M at 100% polymerization.

(Note-2) Amount of coagulum: 150) Filtered through a mesh wire mesh, washed the filtration residue with water, and dried at 180"Q for 5 hours to obtain a coagulum. The amount of dry matter M was calculated as the weight based on the monomer used. I was shocked at %.

(Note-a) Mechanical stability of the emulsion Take 200g of the polymer emulsion in a beaker and mix it with a homomixer for 10 minutes.
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 180°C for 6 hours. The weight of the dry matter was expressed as a percentage of the weight of solids in the collected emulsion.

(Note-4) Chemical stability solid content of emulsion 0.54
Coagulate 60ml of polymer emulsion diluted with water.
The capacity (m
e) It was hail.

1m-5) Polymer emulsion diluted with water to a foamable solids content of emulsion of 8%: / 8
0 me 'k 100- Take a cylinder with a stopper,
It was shaken vigorously 10 times and the amount of foam (me) after 5 minutes was determined.

(Note-6) Water resistance of film - The polymer emulsion was spread on a slide glass and dried at 60° C. for 8 hours and then at 20'Q for 24 hours to create a film with a thickness of 0.2 cm. The water resistance of this film was determined by JIS K-
6828 water drop test method.

(Note 7) Film Adhesion 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-8) Freeze-destroy the COD polymer emulsion in the emulsion waste liquid by freezing it at -10°C for 24 hours,
After melting in SOoC, the polymer was distributed door to door. COD of P liquid is J
Measured according to IS K0102-1971.

〔Effect of the invention〕

The modifier of the present invention has good compatibility with the monomer to be polymerized and can yield a uniform polymer. In addition, the polymerization rate of the monomer increases to the same level or higher than that of known modifiers made of anionic monomers; a polymer with improved performance (degree of polymerization, dyeability, antistatic property, etc.) can be obtained. the resulting polymer emulsion has excellent mechanical and chemical stability and low foaming; the films and coatings obtained from the polymer emulsion have excellent water resistance and adhesion; It produces effects such as

In addition to the above effects, the modifier of the present invention does not have devitrification; imparts hydrophilicity; does not allow flakes, oil, grime, and nano-dirt to adhere to it; and even if it does adhere, it can be easily removed. It also has the effect of providing a polymer emulsion with the following performance properties: the amount of coagulum during polymerization is small, and when the polymer is extracted from the emulsion, almost no emulsifier flows out into wastewater. play.

The modifier of the present invention has superior salt resistance and hydrolysis resistance compared to esters of alcohols having an aromatic nucleus and (meth)acrylic acid or sulfuric esters of alkylene oxide adducts of (meth)acrylic acid. There is.

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

Emulsions of these polymers can also be used for the production of adhesive, coating, impregnating and dispersing compositions, water-based paint adhesives, paper processing, W & textile processing (sizing agents, binders for non-woven fabrics, etc.) It can be advantageously used for purposes such as fiber modification, floor polishing, soil erosion prevention, and mixing with concrete and mortar. Furthermore, it can be used in the production of synthetic resins such as polyvinyl chloride and ABS resin, synthetic rubber, and synthetic fibers.

Claims (1)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R is hydrogen or a methyl group. X is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or -CH_2O-.A is an alkylene group having 2 to 4 carbon atoms.n is
It is an integer greater than or equal to 2. l is an integer of 2 or more. M is 1
It is a valent or divalent cation. m is an integer of 1 to 2 and represents the valence of the cation M. ) A modifier for polymers consisting of a sulfonic acid (salt). 2. The modifier according to claim 1, wherein two or more oxypropylene groups are present in the n oxyalkylene-(AO)- groups. 3. 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 ▼ (1) (In the formula, R is hydrogen or a methyl group. n is
It is an integer greater than or equal to 2. l is an integer of 2 or more. M is a monovalent or divalent cation. m is an integer of 1 to 2 and represents the valence of the cation M. ) A method for modifying a polymer, characterized by using a sulfonic acid (salt) represented by: 4. The modification method according to claim 3, wherein two or more oxypropylene groups are present in the n oxyalkylene-(AO)- groups. 5. Sulfonic acid (salt) 0.1 based on the total weight of monomers
The modification method according to claim 3 or 4, wherein ~80% is used. 6. The modification method according to any one of claims 3 to 5, which comprises emulsion polymerizing an ethylenically unsaturated monomer in the presence of a sulfonic acid (salt).