JPS6210102A - Reactive emulsifier - Google Patents

Abstract

PURPOSE:A reactive emulsifier which can give a polymer which can form a film having improved water resistance and solvent resistance without lowering the rate of polymerization of an unsaturated compound, comprising a sulfate ester (salt) having a specified structural formula. CONSTITUTION:A reactive emulsifier comprising a sulfate ester (salt) of the formula (wherein X is an at least trihydric polyalcohol residue, A is a 2-4 C alkylene or aryl-substituted alkylene, R is H or CH3, M is a cationic counter ion, l is an integer >=2, m is an integer >=1, n is 0 or an integer >=1 and a, b and c are each 0 or an integer of 1-150). A film or coating of an emulsion polymer obtained by using this emulsifier exhibits excellent water resistance and adhesiveness and possibility of improved solvent resistance. An emulsion obtained by incorporating this emulsifier can show excellent stability and can be improved also in long-term storage and freeze-thaw property. This emulsion can be applied to wood, metal, paper, concrete or the like by a process such as bonding, coating or impregnation and can be used as an antistatic agent for fiber, a dyeing aid or a sizing agent.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to reactive emulsifiers.

[Conventional technology]

By using a reactive emulsifier as an emulsifier for aqueous emulsion polymerization of polymerizable unsaturated compounds, it is possible to improve the water resistance of the resulting polymer film, and to prevent the emulsifier from remaining in waste water when breaking the emulsion and taking out the polymer. There are techniques that attempt to incorporate reactive emulsifiers into polymers to overcome the problem of contamination. For example, a method using itaconic acid varnish f IV sulfonate (Japanese Patent Publication No. 46-34
894) and a method using an acrylamide derivative having an amide group containing a polyalkylene oxide chain (Japanese Patent Application Laid-open No. 786/1986).

[Problem that the invention seeks to solve]

However, these methods are not satisfactory in terms of reactivity and emulsion stability, and in particular, there are problems in that the polymer films prepared from the resulting polymer emulsions do not have sufficient water resistance and solvent resistance. There is.

[Failure to solve the problem]

The present inventors have developed a reactive emulsifier that does not cause a decrease in the polymerization rate of unsaturated compounds to be polymerized. .A.
is an alkylene group having 2 to 4 carbon atoms or an aryl group-substituted alkylene group. R is a hydrogen atom or a methyl group. M is a cationic counterion. l is an integer greater than or equal to 2,
m is an integer of 1 or more, and n is O or an integer of 1 or more.

aFblc is 0 or an integer from 1 to 150. ) is a reactive emulsifier consisting of a sulfuric acid salt (salt).

In the general formula (1), the polyhydric alcohol that produces the polyhydric alcohol residue
(chrycerin, trimethylolpropane, etc.), polyhydric alcohols with a valence of four or more (pentaerythritol, sorbitan, sorbitol, sucrose, etc.), and mixtures of two or more of these.

Among these, preferred are trivalent to octavalent polyhydric alcohols, and particularly preferred are trivalent to tetravalent polyhydric alcohols.

The alkylene group having 2 to 4 carbon atoms in A is an ethylene group,
Examples of the aryl-substituted alkylene group include a propylene group, a butylene group, and a phenyl-substituted ethylene group from tyrene, a phenyl-substituted methylethylene group from α-methylstyrene, and the like. Among these, preferred are alkylene groups having 2 to 4 carbon atoms, and particularly preferred are alkylene groups having 2 or 3 carbon atoms. These 7) v-kylene groups form an oxyalkylene group together with an oxygen atom to form a polyoxyalkylene chain, but the oxyalkylene groups in such a polymerization chain may be of the same type or of different types (in this case, The combination format may be block, random, etc.). Among the oxyalkylene groups, preferred are an oxyethylene group, an oxypropylene group, and a combination group (block, random) of an oxyethylene group and an oxypropylene group.

Cationic counterions of M include hydrogen atoms, alkali metals, ammonium and amine cations.

Examples of alkali metals include sodium and potassium. Examples of the amine cation include alkanolamine cations and lower alkyl (1 to 4 carbon atoms) amine cations. Among these, alkali metals and ammonium are preferred.

1+m is usually 3-6, preferably 3-4.

When l+m is less than 3, the emulsion obtained by polymerization:/(
Dmo/mer polymerization: i4 or the water resistance of the emulsion film decreases, and if it exceeds 6, the stability of the emulsion obtained by polymerization decreases.

Furthermore, if l is less than 2 in general formula (1), the water resistance and solvent resistance of the resulting emulsion film will decrease. When m is less than 1, the stability of the obtained emulsion decreases.

Specific examples of the sulfuric acid ENT/I/(salt) represented by the general formula (1) include the following.

(a) Di(meth)acrylate Nnl of trihydric alcohol or its alkylene oxide adduct: EO/PO (2/8') of dimethacrylate of glycerin
Monosulfate sodium salt Nn2:) Limethylolpropane EOQ5 dimethacrylate monosulfate potassium salt N[18: Glycerin PO (a) EOα valley monoacrylate monomethacrylate monosulfate enuterammonium salt Nn4: Glycerin PO (9) EO (6) Nosimethacrylate monosulfate ester sodium salt NcL5 Dimethacrylate monosulfate ester ammonium salt of nitrimethylolpropane, etc. (b) (meth)acrylate sulfate ester salt N (16 : Pentaerinurito/l/EO(B
Diacrylate monosulfate sodium salt of PO(2) Nn? : Tsurpitou 1v PO(6(I EOC1
) of dimethacrylate disulfate sodium salt N[L8: Trimethacrylate monosulfate sodium salt of pentaerythritol PO (c) Nn9:
Pentaerinurito) v EO/PO (12/1
The sulfuric acid ester (salt) represented by the general formula (1), such as the dimethacrylate disulfate sodium salt of After adding alkylene oxide to , the alkylene oxide is converted into a sulfuric acid ester using a sulfating agent (oleum, sulfuric acid, chlorosulfuric acid, nulphamino acid, etc.), and neutralized if necessary. It can be produced by a method of esterifying with and/or methacrylic acid, sulfuric acid esterifying the remaining hydroxyl groups with the above-mentioned sulfating agent, and neutralizing if necessary.

A polymer emulsion can be produced by emulsion polymerization using the emulsifier of the present invention, in which case the amount of the emulsifier used is usually 01 to 20% as an active ingredient relative to the monomer to be polymerized.
01-20% by weight or 0.5-10% by weight.

Various monomers can be used for aqueous polymerization to which the emulsifier of the present invention is applied; examples include vinyl ester monomers such as vinyl acetate; (meth)acrylic acid, methyl (meth)acrylate, and ) Ethyl acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)arylate, (meth)acrylonitrile, (meth)acrylamide, etc. carboxyl group, ester group, nitrile group,
Acrylic monomers containing amide groups; Aromatic hydrocarbon monomers such as styrene and divinylbenzene; Conjugated diolefins such as butadiene, isoprene, and chloroprene; Hydrocarbon monomers containing nitrogen such as vinyl chloride and vinylidene chloride; Fats such as ethylene group hydrocarbon monomer;
Examples include unsaturated polycarboxylic acids such as maleic acid and methyl maleate, or esters thereof, and two or more thereof. Among these, preferred are vinyl ester monomers, acrylic monomers, aromatic hydrocarbon monomers, and 2-logen-containing hydrocarbon monomers. As the polymerization initiator and accelerator, known ones may be used. For example, as the initiator, hydrogen peroxide, potassium persulfate, ammonium persulfate, sodium peroxide, t-butyl hydroperoxide, azobisisobutyl Examples include lonitrile, azobisisobutyronitrile, and the like. Monosodium hydrogen sulfite, sodium thiosulfate, ferrous ammonium sulfate, copper sulfate, and the like may be used as accelerators.

The method for carrying out emulsion polymerization using the emulsifier of the present invention may be similar to conventional methods. During the polymerization, other emulsifiers may be added as necessary, such as alkyl sulfates, alkylar I)
/L/ Anionic surfactants such as sulfonates or fatty acid salts, alkylary-nonpolyoxyethylene or pluronic type nonionic surfactants can be used in combination, but if used in large amounts, this will go against the purpose of the present invention. Therefore, it is preferably 50% or less of the weight of the emulsifier of the present invention.

The polymerization temperature varies depending on the type of monomer to be polymerized, the emulsification state, etc., but is usually -5 to 100°C. Furthermore, in addition to water as a commonly used aqueous medium, an organic solvent such as methanol, isopropanol, or acetone may be used in combination, and it may be preferable to use a polymerization regulator such as mercaptan.

〔Example〕

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

Example 1 To an esterification reactor equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, 1,000 mJ% of toluene and 878 g (1 mo/l) of glycerin PO(9) EO(6) were added.
/ ), 172 g of methacrylic acid (2 mo/I/), 17 g of hydroquinone and 10 g of parat IV en sulfonic acid
was charged and refluxed until about 369 g of water was removed. After washing with aqueous caustic soda solution and removing toluene under reduced pressure, pale yellow glycerin PO(9) EO(6)
of dimethacrylate was obtained. This dimethacrylate) 1
．． 014g (1 mo/L/) of ethyl dichloride72,000
116.5 g (1 mole) of chlorosulfuric acid was added dropwise at 20° C. while blowing air, and after sulfuric acid esterification, 40.0 g of caustic soda was added. An aqueous solution of li+ (1 mo/I/) was added to neutralize. Ethane dichloride was removed under reduced pressure and filtered. Yellow glycerin PO(9) EO(6) dimethacrylate monosulfate ester sodium salt (sulfuric acid ester described in #J vN+14) was obtained in quantitative yield.

Example 2 Pentaerythol/l/ was prepared in the same manner as in Example 1.
EO/PO (1vt2) 1.360,! i' (1
% 7L/ ) and methacrylic acid/acid 172g (2mol/L
/) and chlorosulfate 2+8p(2mo)V
) with caustic soda 80.9 (2 mo/
v), neutralized with pentaerythol EO/PO (12/1
2) Dimethacrylate disulfate ester sodium salt (
The ethel sulfate salt Nn9) mentioned above was obtained in quantitative yield.

Test Example 1 270 g of ion-exchanged water was placed in a reaction apparatus equipped with a stirrer, a dropping funnel, a nitrogen inlet, a thermometer, and a reflux condenser. The emulsifier of the present invention (Examples 1 and 2) 7.2. ! i! , 0.36 g of sodium bicarbonate, and 0.36 g of ammonium persulfate.
9.9 was charged, and after nitrogen purging, a mixed monomer of styrene 99p and butyl acrylate 81J was added dropwise from the dropping funnel over 2 hours at 65 to 70''C under stirring to perform polymerization.
A good milky white emulsion with a monomer polymerization conversion rate of 99.5% or more was obtained.

Table 1 shows the test results for the water resistance and solvent resistance of the film made from the emulsion; the mechanical stability and freezing stability of the emulsion.

Table-1 (Note-1) Comparative Example 1 A water-resistant emulsion of glycerin PO (91EO(a) monomethacrylate monosulfate ether sodium salt (Note-2) film was spread on a slide glass and heated to 60°C for 80 minutes.
0.211 after drying for 24 hours at 20°C.
A film with a thickness of m was produced. The water resistance of this film was tested according to the water drop test method of JIS K-6828.

(Note-3) Solvent-resistant emulsion film of the film was subjected to benzene extraction for 48 hours, and the insoluble matter obtained was dried and weighed against the weight of the emulsion film used as the sample. It hailed.

Q4E-4) Mechanical stability of emulsion Take emulsion 200.9 in a beaker and mix in a homomixer for 10.
After stirring at 0.00 rpm for 30 minutes, the resulting coagulated material was separated using a 150-mesh wire mesh, washed with cold water, and then dried. This dry weight was calculated based on the weight of solids in the collected emulsion.

(Note-5) Freeze stability of emulsion Add 50g of emulsion to galanupin and seal it.
One cycle was 12 hours at 35°C and 12 hours at 35°C, and the number of times it took for the emulsion to freeze was measured.

〔Effect of the invention〕

When the emulsifier of the present invention is used, compared to conventional reactive emulsifiers, internal crosslinking of the polymer progresses in the emulsion particles and the polymerization rate of the monomer increases, so the physical properties of the resulting polymer are improved. For example, the emulsion polymer films or coatings obtained according to the present invention exhibit excellent water resistance and adhesion;
Furthermore, it has the effect of making it possible to improve solvent resistance, which could not be achieved with films etc. obtained from conventional reactive emulsifiers.

Emulsions obtained by incorporating the emulsifier of the present invention have excellent stability, and long-term storage and freeze-thaw properties are also improved. In addition to the above-mentioned effects, the resulting polymer film has no devitrification, is hydrophilic, and can be easily removed by stains such as flakes, oil, and grime. It has the following performance. When the polymer is still extracted from the emulsion, the emulsifier hardly flows out into the wastewater.

Claims (1)

[Claims] 1. General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, X is a trivalent or higher polyhydric alcohol residue.A
is an alkylene group having 2 to 4 carbon atoms or an aryl group-substituted alkylene group. R is a hydrogen atom or a methyl group. M is a cationic counterion. l is an integer greater than or equal to 2,
m is an integer of 1 or more, and n is 0 or an integer of 1 or more. a, b, and c are 0 or an integer of 1 to 150. ) A reactive emulsifier characterized by consisting of a sulfuric ester (salt). 2. The reactive emulsifier according to claim 1, wherein the sum of l and m in general formula (1) is in the range of 3 to 6.