JPH0798845B2 - Reactive modifier - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a reactive modifier.

[Prior Art] Conventionally, for example, a polymer such as (meth) acrylonitrile (abbreviation of acrylonitrile and / or methacrylonitrile; hereinafter, the same expression is used), (meth) acrylic acid or a salt or ester thereof, vinyl chloride, vinylidene chloride. Alkylene oxide adducts of aromatic ring-containing alcohols and (meth) acrylic acid as nonionic hydrophilic group-containing unsaturated compounds used as reactive modifiers for polymers of ethylenically unsaturated monomers such as styrene and Are known.

[Problems to be Solved by the Invention] However, the polymers obtained by these methods do not necessarily have sufficient surface hydrophilicity, and the water resistance and adhesiveness of a film prepared from an emulsion obtained by use in emulsion polymerization Is not always sufficient.

[Means for Solving the Problems] The present inventors have imparted excellent hydrophilicity to the surface of a polymer, and have excellent water resistance and adhesion to a film prepared from an emulsion obtained by use in emulsion polymerization. The present invention has been achieved as a result of extensive studies on a reactive modifier that imparts properties.

That is, the present invention has the general formula [Wherein Z is an aryl group optionally substituted with an alkyl group, an alkaryl group or an aralkyl group, or a linear or branched alkyl group having 1 to 24 carbon atoms optionally substituted with an aryl group, or It is an alkenyl group. R is a hydrogen atom or a methyl group. A is an alkylene group having 2 to 4 carbon atoms which may be substituted with an aryl group. a and c are 0 or an integer of 1 to 50. b
Is an integer of 1 to 50. However, − (AO) _a −, − (AO)
The content of oxyethylene chains in the total weight of the chains represented by _b- and-(AO) _c- is 10 to 100% by weight. ] It is a reactive modifier for the polymer of the ethylenically unsaturated monomer which consists of a nonionic hydrophilic group containing unsaturated compound shown by these.

In the general formula (1), the alkyl group of Z, the aryl group which may be substituted with an alkaryl group or an aralkyl group is a phenyl group, o-, m-, p- or a mixed crezoyl group, a xylenoyl group, propylphenyl. Group, isopropylphenyl group, butylphenyl group, sec-butylphenyl group, t-butylphenyl group, di-t-butylphenyl group, t-amylphenyl group, octylphenyl group, 2-ethylhexylphenyl group, dioctylphenyl group, Examples thereof include nonylphenyl group, dinonylphenyl group, dodecylphenyl group, methyldiphenyl group, trimethyldiphenyl group, styrenated phenyl group, styrenated crezoyl group, styrenated xylenoyl group and benzylated phenyl group.

The linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms which may be substituted with an aryl group is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a t- group. Butyl group, pentyl group,
t-amyl group, hexyl group, heptyl group, octyl group,
2-ethylhexyl group, nonyl group, decyl group, dodecyl group, tridecyl group, myristyl group, stearyl group, oleyl group, cetyl group, benzyl group, phenethyl group and the like can be mentioned.

In the alkylene group having 2 to 4 carbon atoms which may be substituted with an aryl group of A, the alkylene group is an ethylene group, a propylene group, a butylene group or the like, and the aryl group-substituted alkylene group is a phenyl-substituted ethylene group derived from styrene. , A phenyl-substituted methylethylene group derived from α-methylstyrene, and the like. Of these, preferred are alkylene groups having 2 to 4 carbon atoms, and particularly preferred are alkylene groups having 2 or 3 carbon atoms.

These alkylene groups form an oxyalkylene chain-(AO) _a -,-(AO) _b- and-(AO) _c- with an oxygen atom, but the oxyalkylene chain in such a polymer chain is of the same kind. However, they may be different types (block, random, etc. as the combination form in this case). Preferred among the oxyalkylene groups are an oxyethylene group and a combined group (block, random) of an oxyethylene group and an oxypropylene group.

The content of the oxyethylene chain in the oxyalkylene chain represented by-(AO) _a -,-(AO) _b- and-(AO) _c- is usually 10 to 100% by weight, preferably 30 to 80% by weight. is there.

Specific examples of the compound represented by the general formula (1) are shown in Table-1.
The following are listed.

In the following, E is ethylene oxide, P is propylene oxide, E ₁₀ is an oxyalkylene chain in which 10 mol of ethylene oxide is added, P ₁₀ E ₃₀ is an oxyalkylene chain in which 10 mol of propylene oxide and 30 mol of ethylene oxide are block-added in this order, Bz- Represents a benzyl group, Me represents a methyl group, and BP represents a biphenyl group, and the same description is used below.

The compound represented by the general formula (1) comprises a lower or higher alcohol and / or an alkylphenol, an alkylarylphenol or a phenylalkylphenol or an alkylene oxide adduct thereof and a glycidyl ether of an alkylene oxide adduct of (meth) acrylic acid. The reaction is carried out in the presence of a catalyst such as a borohydride ether complex salt or tin tetrachloride, and if necessary, alkylene oxide is further added by a conventional method (in this case, some transesterification reactions may be involved depending on the number of moles of alkylene oxide added). It can be manufactured by a method such as

Examples of the polymer of the ethylenically unsaturated monomer that is modified using the reactive modifier of the present invention include the following.

(A) Nitrile group-containing monomer: (meth) acrylonitrile and the like.

(B) Ester of unsaturated carboxylic acid [(meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, etc.]: an alkyl group having 1 to 20 carbon atoms (methyl, ethyl, butyl,
Alkyl (meth) having a 2-ethylhexyl group etc.
Acrylate; glycol (ethylene glycol, 1,4
Mono- or di (meth) acrylates of butanediol, polypropylene glycol, etc .; diesters or half-esters of maleic acid, fumaric acid, or itaconic acid.

(C) Amide of unsaturated carboxylic acid: (meth) acrylamide and the like.

(D) Halogen-containing monomer: vinyl chloride, vinylidene chloride, chloroprene, etc.

(E) Aromatic vinyl hydrocarbon monomer: styrene, α-methylstyrene, chlorostyrene, vinyltoluene and the like.

(F) Aliphatic hydrocarbon monomer: ethylene, propylene, butadiene, isoprene and the like.

(G) Vinyl ester or (meth) allyl ester: Vinyl acetate, vinyl propionate, divinyl phthalate, allyl acetate, diallyl phthalate and the like.

(H) Unsaturated carboxylic acid or salt thereof: A polymer composed of (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and salts thereof.

Polymers of these ethylenically unsaturated monomers are synthetic fibers,
It is used as a synthetic resin, synthetic rubber, synthetic resin emulsion and synthetic rubber latex. For example, synthetic fibers include an acrylonitrile type (co) polymer [acrylonitrile of 75% or more and a monomer copolymerizable therewith, such as vinyl acetate, (meth) acrylic acid ester, styrene, vinyl chloride, vinylidene chloride, etc. Copolymers; copolymers of acrylonitrile 35 to 75% with the above-mentioned monomer that can be copolymerized therewith, and the like], and the like, synthetic resins include polystyrene, styrene-acrylonitrile copolymer, ABS resin, (Meth) acrylic resin etc. are mentioned.

The amount of the reactive modifier used in the present invention can be variously changed depending on the kind of the polymer, the composition of the monomer, the purpose, the required performance and the like. In the case of producing a hydrophobic polymer for the purpose of dyeability, antistatic property, etc., the reactive modifier of the present invention is usually contained in the polymer in an amount of 0.1 to 20% by weight, preferably 0.2% by weight.
~ 10% should be included. If it exceeds 20%, the affinity for water becomes too large, which is often inconvenient. On the other hand, in the case of producing a hydrophilic polymer (for example, a water-soluble resin), the reactive modifier of the present invention is usually contained in the polymer in an amount of 2 to 80% by weight, preferably 10 to 60%. It is better to be

Modification of the polymer with the reactive modifier of the present invention can be carried out by various methods. As the polymerization method, bulk polymerization,
Any of solution polymerization, suspension polymerization and emulsion polymerization,
The same polymerization method and polymerization conditions as those of various known (co) polymers can be used.

As a method for initiating the polymerization, a method by irradiation with electron beams, γ-rays or ultraviolet rays, an initiation method by heating and a method by using an initiator can be employed.

In the method using an initiator, examples of the initiator include persulfates (ammonium persulfate, etc.), peroxy compounds (benzoyl peroxide, lauroyl peroxide, hydrogen peroxide, etc.), and azo initiators (azobisisobutyro). Nitriles), redox initiators (sulfites and peroxy compounds, hydrogen peroxide and Fe ²⁺ salts, etc.) and the like.

The polymerization temperature varies depending on the polymer, but is generally 30 to 150 ° C.

In addition, during the polymerization, a medium [a solvent commonly used for solution polymerization; dimethylformamide, dimethylacetamide, dimethylsulfoxide, concentrated aqueous solution of zinc chloride, etc .;
Aqueous media commonly used in emulsion and suspension polymerization;
Water, mixed solvent of water and water-soluble organic solvent (methanol, isopropanol, acetone, etc.)], polymerization regulator [various mercaptans (eg dodecyl mercaptan)]
Such a chain transfer agent] and a dispersant (partially saponified polyvinyl alcohol etc.) can be used if necessary.

When the polymerization is carried out using the reactive modifier of the present invention, it may be mixed in a monomer (mixture) to carry out the polymerization, or may be mixed with a partial polymer, a monomer-polymer mixture or a polymer. It may be grafted or block polymerized. It can also be polymerized on the surface of polymer moldings (fibers, textiles, etc.), films or castings.

The reactive modifier of the present invention is particularly useful as a reactive emulsifier (polymerizable emulsifier) used in emulsion polymerization of monomers. The use as such an emulsifier can be carried out by various methods. For example, in an emulsion polymerization method using an ordinary emulsifier, the reactive modifier of the present invention can be used instead of the ordinary emulsifier. In addition, after the reactive modifier of the present invention or the monomer to be polymerized with the reactive modifier is preliminarily polymerized, the monomer to be further polymerized or the monomer to be polymerized and the reactivity modifier of the present invention are modified. Polymerization can also be carried out by a method of adding a denaturing agent to the polymerization system.

The monomer is not particularly limited as long as it is a monomer capable of emulsion polymerization, and examples thereof include the monomers (a) to (h).

The amount used as an emulsifier varies depending on the composition of the monomer, the purpose of use of the produced emulsion and the required performance, but the nonionic hydrophilic group-containing unsaturated compound represented by the general formula (1) is usually added to the monomer mixture in an amount of 0.05 to 10% by weight, preferably 0.1-5
It is recommended to use the weight%.

In the case of emulsion polymerization, an ordinary emulsifier having no copolymerizability [anionic activator (sodium dodecylbenzene sulfonate, sodium lauryl sulfate ester, sodium alkyldiphenyl ether disulfonate, ammonium polyoxyethylene alkyl ether sulfate ester, etc.) and / Or a nonionic activator (polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polypropylene glycol ethylene oxide adduct, etc.)] can be used in combination, but it is preferable to use a large amount because it is against the object of the present invention. Absent.

In the above-mentioned various polymerization methods, in addition to the modifier of the present invention, other anionic monomers [sulfopropyl (meth) acrylate, styrene sulfonate, alcohol having an aromatic nucleus or its alkyleneoxy adduct and [Sulfonated product of ester with (meth) acrylic acid] can also be used in combination. When used in combination, the amount of the modifier of the present invention is usually 30% or more, preferably 50% or more, based on the total weight of the modifier of the present invention and other anionic monomer.

[Examples] The present invention will be further described with reference to Examples below, but the present invention is not limited thereto.

However, in the following reference example, b is 0 in the general formula (1).
Compounds having the groups in Table 2 were used, except that they were replaced with. In Table 2, P / E _40/20 is propylene oxide 40
A mixture of 20 mol of ethylene oxide and 20 mol of ethylene oxide shows a polyoxyalkylene chain randomly added, and Ph is a phenyl group,
Bz represents an endyl group and St represents styryl, and the same description is used below.

Reference Example 1 The compound No. 5 in Table 2 was used as the reactive modifier of Reference Example 1 to modify the polymer.

After stirring, 150 g of water and ammonium persulfate in a reaction vessel equipped with a dropping funnel, a nitrogen inlet, a thermometer and a reflux condenser.
2 g and 0.3 g of sodium hydrogen carbonate were charged, the system was replaced with nitrogen gas, and the temperature was raised to 70 ° C.

Then, 70 g of butyl acrylate, 30 g of styrene and 1.3 g of the compound No. 5 shown in Table 2 were added dropwise from a dropping funnel under stirring for 3 hours. 0.05 g of ammonium persulfate was added every hour during the dropping. 70 ° C after completion of dropping
The mixture was further reacted for 1 hour to obtain an emulsion. Table 3 shows the performance test results of the produced emulsion and the film produced from the emulsion.

Example 1 and Comparative Examples 1-1 to 1-3 Instead of the compound No. 5 in Table 2 in Reference Example 1, the compound No. 1 in Table 1 was used in Example 1, and in Comparative Example 1-1. Nonylphenol P / E _10/10 methacrylate, in Comparative Example 1-2, nonylphenol E ₁₀ acrylate, and in Comparative Example 1-3, methanol E ₂₃ methacrylate, using the same weight (compound No. 5), respectively, for reference. Polymerization was performed according to the method of Example 1 to obtain each emulsion.

Table 3 shows the performance test results of each produced emulsion and the film produced from the emulsion.

Note) Test method for each test item (1) Monomer polymerization conversion rate Take 1.5 g of the polymer emulsion, measure the evaporation residue weight after drying at 130 ° C for 1.5 hours, and express it in% of the solid content weight at 100% polymerization. did.

(2) Filter through a wire mesh of 150 mesh, wash the filter residue with water, and then
A coagulum was obtained by drying at 30 ° C. for 5 hours. The weight of this dried product was expressed as a weight percentage with respect to the monomers used.

(3) Mechanical stability of emulsion 200 g of polymer emulsion was placed in a beaker and stirred with a homomixer at 10,000 rpm for 30 minutes, and the solidified product was filtered with a 150-mesh wire net and washed with cold water, and at 130 ° C for 5 hours. Dried. The weight of the dried product was expressed as% of the solid content in the collected emulsion.

(4) Chemical stability of emulsion 50 ml of polymer emulsion diluted with water to a solid content of 0.5%
Volume of N / 10CaCl ₂ (ml) required to solidify / separate
Expressed as

(5) Foaming property of emulsion 30 ml of a polymer emulsion diluted with water to a solid content of 3%
The resulting mixture was placed in a 100 ml cylinder equipped with a stopper, shaken vigorously 10 times, and expressed as the amount of foam (ml) after 5 minutes.

(6) Water resistance of film A polymer emulsion was spread on a slide glass and dried at 60 ° C. for 8 hours and then at 20 ° C. for 24 hours to prepare a film having a thickness of 0.2 mm. The water resistance of this film is JIS K
Tested by the water drop test method of -6828.

(7) Film Adhesion The 180 ° peel strength at 40 ° C. between the glass / film (reinforced with cotton cloth) of the film produced by the method of (6) above was measured at a pulling speed of 100 mm / min.

Reference Example 2 The compound No. 7 in Table 2 was used as the reactive modifier of Reference Example 2 to modify the polymer.

To a reaction vessel equipped with a stirrer, a dropping funnel, a nitrogen inlet, a thermometer and a reflux condenser, 1.6 g of compound No. 7 in Table-2, 22 g of vinyl acetate and 18 g of butyl acrylate were charged and uniformly dissolved. Next, 117.5 g of ion-exchanged water and 0.16 g of ammonium persulfate were added and stirred, emulsified, and after nitrogen substitution,
Polymerization was carried out at 75 ° C for 30 minutes with stirring. Continued ion exchange water
134.5 g, compound N0.7 of Table-2 5.6 g, ammonium persulfate 0.56 g, vinyl acetate 77 g and butyl acrylate 63 g
The emulsion consisting of was added dropwise from a dropping funnel over 2 hours, polymerization was carried out at 80 ° C with stirring, 18 g of 1% ammonium persulfate aqueous solution was added, and the temperature was raised to 85 ° C and polymerization was carried out for 2 hours to obtain a uniform emulsion. It was

Table 3 shows the performance test results of the produced emulsion and the film produced from the emulsion.

Reference Example 3 The compound No. 6 in Table 2 was used as the reactive modifier of Reference Example 3 to modify the polymer.

Into a reaction vessel equipped with a stirrer, a dropping funnel, a nitrogen inlet, a thermometer and a reflux condenser, 5 g of compound No. 6 in Table-2 and 100 g of styrene were charged and uniformly dissolved. Next, add 250 g of ion-exchanged water and 0.8 g of benzoyl peroxide, and after thoroughly replacing with nitrogen, sodium sulfite 1% at 25-30 ° C under strong stirring.
20 g of the aqueous solution was added dropwise over 1 hour, and the reaction was further performed at 25-30 ° C for 1 hour to obtain a granular uniform polymer. The granular polymer washed with water and dried was put in a mold and melted at 240 ° C. to obtain a polystyrene resin plate.

The results of measuring the contact angle (hydrophilicity) and surface resistivity of this resin plate with water are shown in Table 4.

Comparative Example 2 A polystyrene resin plate was obtained according to the method of Reference Example 3 except that the same weight of octylphenol E ₁₀ P ₁₀ acrylate was used instead of the compound No. 6 of Table 2 in Reference Example 3. Table 4 shows the measurement results of the contact angle of this resin plate with water and the surface specific resistance.

From Table 4, it can be seen that Reference Example 3 has excellent hydrophilicity due to low contact angle frequency and excellent antistatic property due to low surface resistivity.

Note) Test method for each test item (1) Contact angle The resin plate was washed with cold water and dried at 130 ° C for 2 hours, then measured with a contact angle meter [CA-D type; manufactured by Kyowa Interface Science Co., Ltd.]. did.

(2) Surface resistivity After leaving the resin plate in an atmosphere with a humidity of 60% and a temperature of 20 ° C for 24 hours, the TR-300C manufactured by Takeda Riken Co., Ltd. is used as a power source, TR-42 as an electrode, and TR-8651 as a detector. It was measured with the connected device.

Example 2 The compound No. 2 in Table 1 was used as the reactive modifier of the present invention to modify the polymer.

50 g of methyl methacrylate, 5 g of compound No. 2 in Table 1 and 0.1 g of lauroyl peroxide were uniformly dissolved and charged in a glass mold, and the mixture was polymerized at 65 ° C. for 5 hours. The polymer taken out from the mold after cooling was a glassy resin having a polymerization rate of 99.3% and good transparency. Humidity of this resin is 60%,
After standing in an atmosphere of a temperature of 20 ° C. for 24 hours, the surface resistivity was measured by the method shown in Table 4 and found to be 1.3 × 10 ¹² Ω, which was a good antistatic property.

[Effects of the Invention] The reactive modifier of the present invention imparts excellent hydrophilicity to the surface of a polymer, and also has excellent water resistance and adhesion to a film prepared from an emulsion obtained by use in emulsion polymerization. It is what imparts sex. Further, the obtained emulsion has excellent mechanical stability and chemical stability; low foaming property; small amount of coagulum during polymerization; when polymer is taken out from emulsion, emulsifier in waste water. It also has the effect that it hardly leaks.

Further, the polymerization rate of the monomer is increased to the level equal to or higher than that of a known nonionic monomer modifier; a polymer having improved performance (degree of polymerization, hydrophilicity, antistatic property, etc.) can be obtained. Provides devitrification and antistatic properties; dust, oil,
It also has an effect of giving a polymer having a performance such that dirt such as dust is unlikely to adhere thereto; and even if adhered, it can be easily removed.

The polymer modified with the reactive modifier of the present invention is useful as a synthetic fiber, a fiber treating agent, a synthetic resin, a paper processing agent, a resin for hair spray and the like.

Further, these polymer emulsions can be used for production of compositions for adhesion, coating, impregnation and dispersion, and are used for adhesives for water-based paints, paper processing, fiber processing (paste agents, binders for non-woven fabrics), fibers, etc. It can be advantageously used for applications such as modification, floor polish, soil erosion prevention, and concrete and mortar admixture. Further, it can be used for producing polyvinyl chloride, synthetic resin such as ABS resin, synthetic rubber, synthetic fiber and the like.

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Claims (1)

[Claims] 1. A general formula [Wherein Z is an aryl group optionally substituted with an alkyl group, an alkaryl group or an aralkyl group, or a linear or branched alkyl group having 1 to 24 carbon atoms optionally substituted with an aryl group, or It is an alkenyl group. R is a hydrogen atom or a methyl group. A is an alkylene group having 2 to 4 carbon atoms which may be substituted with an aryl group. a and c are 0 or an integer of 1 to 50. b
Is an integer of 1 to 50. However, − (AO) _a −, − (AO)
The content of oxyethylene chains in the total weight of the chains represented by _b- and-(AO) _c- is 10 to 100% by weight. ] It consists of the nonionic hydrophilic group containing unsaturated compound shown by these, The reactive modifier for polymers of the ethylenically unsaturated monomer characterized by the above-mentioned.