JPH03707A - Preparation of polymerization modifier and polymer - Google Patents

Abstract

PURPOSE:To obtain a polymn. modifier which does not act as a source of bad odor of a polymer after polymn. and does not spoil heat storage resistance of the formed polymer by specifying a structure, a number-average MW and the number of ethylenic double bonds of the ends of the molecular main chain of a styrene polymer. CONSTITUTION:A styrenic monomer is reacted, if necessary, in the presence of a polymn. initiator and if necessary, in 10-1,000% solvent based on the monomer in an inert gas atmosphere and under ordinary or elevated pressure at 150-240 deg.C for 1-50hr to obtain a polymn. modifier consisting of a styrenic polymer contg. a polymer of the formula (wherein A is styrenic polymer residue; X is H, a lower alkyl, OH, an acetoxy, a lower alkoxy or a halogen), having a number-average MW of 500 or larger and contg. 0.05-0.9 ethylenic double bond on average per molecule at the ends of the molecular main chain. A vinyl polymer is obtd. by polymerizing a vinyl monomer in the presence of 1-50wt.% said polymn. modifier based on the whole monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a polymerization regulator and a method for producing vinyl polymers.

C. Prior Art] Conventionally, chain transfer ljl agents such as mercaptan compounds, 2.
There are low molecular weight 2,2-disubstituted olefins such as 4-diphenyl-4-methylutopentene.

[Problems to be Solved by the Invention] However, in the former case, an odor source remains in the polymer unless the mercabutanization step is sufficiently carried out after the polymerization is completed.

If the latter remains in the polymer, there is a problem in the heat-resistant storage stability of the polymer.

[Means for Solving the Problems] The present inventors have made extensive efforts to develop a polymerization modifier and a method for producing vinyl polymers that do not become a source of odor in the compound produced after polymerization and do not impair the heat-resistant storage stability of the produced polymer. As a result of consideration,
We have arrived at the present invention. That is, the present invention contains a polymer represented by the general formula (wherein A is a styrene polymer residue, and X is hydrogen, a lower alkyl group, a hydroxyl group, an acetoxy group, a lower alkoxy group, or a halogen group). ,
A polymerization modifier comprising a styrenic polymer having a number average molecular weight of 500 or more and having an average of O,OS to 0.3 ethylenic double bonds per molecule at the end of the main chain of the molecule, and claims. This is a method for producing a polymer, characterized by polymerizing a vinyl monomer in the presence of the polymerization regulator described in 1 or 2.

In general formula (1), the lower alkyl group of X is an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, etc.),
Examples of lower alkoxy groups include alkoxy groups having 1 to 4 carbon atoms (such as methoxy groups), and examples of halogen groups include chlorine and bromine.

In the general formula (1), examples of the styrene polymer constituting the styrene polymer residue of A include (co)polymers of styrenes.

Styrenes include styrene, lower alkylstyrene (
o-, +e- or p-methylstyrene, p-ethylstyrene, p"'n-butylstyrene, p-tart
-butylstyrene, etc.), P-acetoxystyrene, P
-methoxystyrene, 0-chlorostyrene, and the like.

Among the styrene polymers constituting the residue of A, polystyrene is preferred.

The polymer represented by the general formula (1) can be produced by bulk polymerization, solution polymerization, or the like.

A polymerization initiator may or may not be used. When used, the polymerization initiator is an organic peroxide initiator (di-t-
butyl peroxide) and azo initiators (2,2
'-7 zopis isoptilonitrile, etc.).

In the case of solution polymerization, the solvent is an aromatic hydrocarbon solvent (
Examples include toluene, xylene, etc.), chlorine solvents (chloroform, ethylene dichloride, ethylene tetrachloride, etc.), ether solvents (1,4-dioxane, etc.), and mixed solvents of two or more of these.

The amount of solvent used is usually 10 to 10% based on the total weight of monomers.
100%, preferably 30-400%.

The polymerization reaction is usually carried out in an atmosphere of an inert gas such as nitrogen under normal pressure or increased pressure. Polymerization temperature is usually 150-240℃
, preferably 180 to 230°C. The reaction time is usually 1 to 50 hours, preferably 2 to 20 hours.

In the case of solution polymerization, a solvent is used after polymerization. Solvent removal is performed under normal pressure or reduced pressure.

The number average molecular weight of the polymer of general formula (1) is usually 500 or more, preferably from too to tooo. If the number average molecular weight is less than 500, heat resistant storage stability will be poor, and too
If it exceeds o, the polymerization adjustment effect becomes small.

The polymerization modifier of the present invention may be a mixture of various polymers. This product usually has an average of O,OS~0.9 ethylenic double bonds at the end of the molecule, preferably an average of O,1#0.7.
Contains. If the number of double bonds is 0.05, the effect as a polymerization regulator will be reduced, and if it exceeds 0.9, the polymerization rate will be too slow.

- The average number of ethylenic double bonds at the end of the main chain of the molecule Y is the integrated intensity of the two protons of the ethylenic double bond at the end of the main chain of the molecule determined by nIR. Let b be the proton integrated intensity of n≦5),
When the number average molecular weight (in terms of styrene) determined by gel permini-sheen chromatography (hereinafter abbreviated as GPC) is 1lln, a polymer residue of formula (3) containing one or more monomers or n or A is obtained. The weighted average number of protons between one or more monomers and -C=CH*

The molecular weight distribution of the polymer serving as a polymerization regulator [expressed as the ratio of weight average molecular weight to number average molecular weight (Mv/In) is usually 2 to 10.

Using the polymerization modifier of the present invention, vinyl monomers can be polymerized to produce vinyl polymers. Vinyl monomers for producing vinyl polymers include styrenes or mixtures thereof with other monomers.

Examples of the styrenes include those described in the section on polymerization regulators, and the preferred ones are also the same.

Other monomers include (meth)acrylic acid esters [alkyl (meth)acrylates, alkyl carbon atoms ranging from carbon number I8 to I8, such as methyl (meth)acrylate,
Ethyl (meth)acrylate, n- or de-butyl (
meth)acrylate, n-octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate, etc.; Hydroxyl group-containing (meth)acrylates such as hydroxyl ethyl(meth)acrylate, amino group-containing (meth)acrylates such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, etc.], vinyl esters (vinyl acetate, vinyl propionate, etc.), aliphatic hydrocarbon vinyl monomers (butadiene, etc.), nitrile compounds (acrylonitrile, methacrylonitrile, etc.), vinyl ethers (vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, etc.), vinyl ketones (vinyl methyl ketone, vinyl hexyl ketone, etc.),
Tovinyl compounds (tovinylvirol, tovinylcarbazole, tovinylindole, tovinylindole, etc.)
, vinyl halides (vinyl chloride, etc.).

Among these, (meth)acrylic acid Nester is preferred, and methyl (meth)acrylate, ethyl (meth)acrylate, n- or t-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are particularly preferred.

In order to obtain a polymer with a higher molecular weight during polymerization, a polyfunctional monomer having at least two polymerizable double bonds [
For example, di- or polyvinyl compounds (divinylbenzene,
Divinyltoluene, ethylene glycol diacrylate, 1. B-hexanediol di-acrylate, etc.)
] can be added. Preferred are divinylbenzene and 1,11-hexanediol diacrylate.

The amount of each monomer in the monomer mixture is typically 40 to 10 styrenes based on the fffffi of all monomers.
0%, preferably 100% of 5ONO, and other monomers usually 80-0%, preferably 5ONO%. Among other monomers, (meth)acrylic acid ester is usually 0 to 80%
, preferably 0 to 40%, other monomers usually 10%
%, preferably 5% or less, polyfunctional monomers usually 3x or less, preferably 1% or less.

Examples of polymerization methods include bulk polymerization, suspension polymerization, and solution polymerization. Suspension polymerization is preferred.

Suspension polymerization can be carried out by stirring the monomer in water containing a dispersion stabilizer, dispersing it, and polymerizing it.

Dispersion stabilizers include water-soluble polymers (gelatin, gum tragacanth, starch, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylates, etc.), poorly soluble fine powder inorganic compounds (barium sulfate, Calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, calcium phosphate, talc, bentonite, diatomaceous earth, clay, etc.), and the amount of dispersion stabilizer used is usually 0°01 to 10 liters based on the weight of water.
%, preferably 0.1 to 5%.

The amount of the polymerization regulator used in the present invention is usually 1 to 50%, preferably 5 to 40%, based on the weight of all monomers. If the amount used is less than 1%, the polymerization rate adjustment effect will be small;
If it exceeds 0%, the particle size of the suspension droplets becomes large.

Radical initiators used in suspension polymerization include easily soluble monomers, including oil-soluble peroxides (benzoyl peroxide, lauroyl peroxide, etc.)
or azo polymerization initiators (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile, etc.).The amount of radical polymerization initiator used is Usually 0.1 based on weight of monomer
-10%, preferably 0.5-5%.

Suspension polymerization is carried out under a nitrogen atmosphere with stirring. Polymerization temperature is usually 40-140°C, preferably 60-120°C
It is. Polymerization time is usually 2 to 20 hours, preferably 4 to 20 hours.
It is lO time. After the polymerization is completed, a vinyl polymer can be obtained by washing with water, filtration, and drying under reduced pressure.

The polymerization conversion rate of the vinyl polymer obtained is usually 95 to 10
0%, preferably 99.9-100%.

The number average molecular weight of vinyl polymers is usually 4,000 to 20
It is 0.000.

The glass transition point is usually 40°C or higher, preferably 50°C or higher.

The molecular weight distribution of vinyl polymers is usually 5 or more.

[Example] The present invention will be further explained below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. In the following, parts indicate parts by weight.

The equipment, conditions, and method used for measurement are as follows.

HR: (Equipment) VARIAN IFISTRUXE
Manufactured by IIT LTD ML-300 (conditions) Solvent CD
C1* (manufactured by Llerck) Sample concentration 8% by weight Internal standard Trimethylsilane The integrated intensity a of the proton at the terminal double bond of the main chain is 4°B ~ 5
．． The integral value between 2 PPM and the integrated proton intensity of the phenyl group is taken between 6.1 and 7.5 PPM.

apc:C device) manufactured by Toyo Soda ■LC-802A (conditions) Column TSK gel 0MH82 (manufactured by Toyo Soda)
Measurement temperature: 40°C Sample solution: 0.5% by weight T[lF solution Injection amount: 2
00 μl Detector Refractive index detector A molecular weight calibration curve was created using standard polystyrene.

Tetrahydrofuran (hereinafter abbreviated as TIIF) undissolved powder measurement method A sample was heated and dissolved in 100 times TIIF under reflux (
swell), filter and weigh the undissolved powder.

Between L THF insoluble decomposition) = -X t o.

[However, S is the sample ffi (g), L is the dry weight (g) of the glass filter filled with Celite 545 (manufactured by Nacalai Tesque ■) used for filtration, and is the dry weight (g) of the glass filter after filtration. ].

Example 1 2,700 parts of xylene was charged into an IQIJ liter sealed reaction vessel equipped with a reflux condenser and a stirrer, and the vessel was purged with nitrogen. After the container was sealed and the pressure inside the system was reduced to 100■■Hg, the liquid temperature was brought to 160°C. A mixed solution of 3,230 parts of styrene, 1,340 parts of xylene, and 129 parts of di-t-butyl peroxide was injected under pressure over 6 hours to polymerize the 111i while maintaining the temperature at 0°C. The temperature was maintained at the same temperature for an additional 30 minutes to complete polymerization. After the polymerization was completed, xylene was removed under reduced pressure. The number average molecular weight of the obtained polymer was 2,400.

The ratio of the proton integrated intensity of the phenyl group of HNMH to the proton integrated intensity on the terminal double bond of the main chain was 480/1. Each molecule has an average of 0.12 ethylenic double bonds at the end of the main chain.

This polymer is referred to as regulator (I).

Example 2 1.0 with stirring device! +7) 0.1 in a sealed reaction vessel
370 parts of a polyvinyl alcohol aqueous solution of 2% PVA235 [1$1 manufactured by Kuraray Co., Ltd.] was charged. 159 parts of styrene,
n-butyl acrylate 51 K, divinylbenzene [
[manufactured by Sankyo Kasei Kogyo ■] 1.0 parts, regulator (I) 90 parts, Nai/Sun-Bf [manufactured by NOF ■, hydrous benzoyl peroxide] 4° 8 parts, and Perbutyl 2 (manufactured by NOF ■,
1.5 parts of t-butyl/(-oxybenzoate) was mixed and dissolved, and this solution was charged into the above-mentioned reaction vessel, and the mixture was replaced with nitrogen while being dispersed and suspended under stirring. Under stirring,
After increasing the temperature to 80°C and holding it at 80°C for 8 hours, the temperature was increased to 90°C.
The temperature was raised to 90° C. for 4 hours to polymerize. 1 more
After raising the temperature to 20°C, it was held at 120°C for 5 hours to complete polymerization. At this time, the polymerization rate of styrene 3 hours after reaching 80°C was 90%, which was slower than the polymerization rate in Comparative Example 1, which will be described later. The polymerization rate was determined by quantifying the residual monomer in the polymerization suspension using gas chromatography. The obtained polymerization slurry was filtered in a conventional manner, washed with water, and dried at 40°C to obtain a vinyl polymer. Furthermore, the THFHF-insoluble condensation content of the vinyl polymer obtained by drying was 3%, which was smaller than the TEIF-insoluble hair of Comparative Example 1, which will be described later.

Comparative Example 1 Polymerization was carried out in Example 1 except that the polymerization temperature was changed to 140° C. and the amount of di-t-butyl peroxide was changed to 266 parts.

The number average molecular weight of the obtained polymer was 2200, and b/a in Example 1 was 248 G/1. There are an average of 0.02 ethylenic double bonds at the end of the main chain per molecule. This polymer was designated as comparative regulator (I').

The same operation was carried out by replacing the regulator (I) of Example 1 with the comparative regulator (E'). At this time, the styrene polymerization rate 3 hours after reaching 80°C was 97%. In addition, the 711F insoluble content of the vinyl polymer obtained by washing with water and drying was 46
%Met.

Example 3 In a 10 IJ liter sealed reaction vessel equipped with a reflux condenser and a stirrer, 180% of the comparative regulator (I',) described in Comparative Example 1 was added.
0 part was added, and the temperature was raised to 180° C. under a nitrogen atmosphere by neglecting soldering to melt the comparative regulator (process). Subsequently, the temperature was raised to 220° C. while stirring, and while maintaining the temperature at 220° C., 84 GG parts of styrene was added dropwise over 12 hours to polymerize. The temperature was further maintained at the same temperature for 1 hour and 30 minutes to complete the polymerization.

After the polymerization was completed, residual monomers were removed under reduced pressure. Additionally, xylene was removed under reduced pressure. The number average molecular weight of the obtained polymer was 2
300, and the b/a in the battle of Example 1 was 837I.

There are an average of 0.87 ethylenic double bonds at the end of the main chain per molecule. This polymer is used as a regulator (■).

Example 4 A vinyl polymer was obtained by carrying out the same operation as in Example 1 except that the regulator (I) was changed to the regulator (n). At this time, 80
The polymerization rate of styrene 3 hours after reaching ℃ is 60%,
The polymerization rate was slower than in Comparative Example 1 and Example 1. Furthermore, the TIIF-insoluble components of the vinyl polymer obtained by drying were dissolved.

The dried polymer was pulverized to 30 μm or less using a jet mill PJ old 00 (manufactured by Nippon Ichi Nematic Co., Ltd.).
Fine powder of 5 μm or less was removed from the finely ground material using an air classifier MDS (manufactured by Nippon Pneumatic Co., Ltd.). 10 pieces of this finely ground material
20g of the sample was collected in a 0nl sample bottle, stored at 50°C for 8 hours, and then sieved through a 42-mesh sieve.The amount of 42-mesh sieve was 3g. The smaller this number is, the better the heat-resistant storage stability is.

Comparative Example 2 The regulator (I) in Example 1 was replaced with a comparative regulator (E),
Add 4.1 parts of Nofumar MSD (manufactured by NOF ■, 2,4-diphenyl-4-methyl-1-pentene), adjust the amount of ethylenic double bonds at the molecular ends in the system, and repeat the same operation. and obtained a vinyl polymer. The polymerization rate of styrene after 3 hours at 80°C was 59%. The 42 mesh in the heat storage test was 18 g, and the heat storage stability was poor.

Example 5 180 parts of xylene was charged into a 11 J liter sealed reaction vessel equipped with a reflux condenser and a stirrer, and the vessel was purged with nitrogen.

After the container was sealed and the pressure inside the system was reduced to 100 mmHg, the liquid temperature was raised to 180°C. 380 parts of styrene, 40 parts of acetoxystyrene, t-
A mixed solution of 29 parts of butyl perbutyl 2 (t-butyl peroxybenzoate manufactured by NOF Corporation) and 80 parts of xylene was pressure-injected over 4 hours to polymerize. The temperature was maintained at the same temperature for an additional 1.5 hours to complete the polymerization. After the polymerization was completed, xylene was removed under reduced pressure. The number average molecular weight (in terms of polystyrene) of the obtained polymer was 2,900.

HNMI? The ratio b/a of the proton integrated intensity of the phenyl group is
was 510/1. Since the molar ratio of styrene and acetoxystyrene is 0.933:0.0Ei7, each molecule has an average of 0.13 main chain terminal double bonds.

This polymer is designated as regulator (III).

Example 6 1.5 with stirring device! 0.1 in a J-ftol sealed reaction vessel.
500 parts of a 2% PVA235 [manufactured by Hl Kuraray, polyvinyl alcohol] aqueous solution was charged. 248 parts of styrene, n
-69 parts of butyl acrylate, 35 parts of modifier (m) and Kayaester IITP-85W (hydrous di-t-butylperoxy-hexahydro terephthalate)1.
0 parts were mixed and dissolved, and this solution was charged into the above-mentioned reaction vessel, and the mixture was replaced with nitrogen while being dispersed and suspended under stirring.

Under a nitrogen atmosphere, while stirring, the temperature was raised to 85°C.
After holding at ℃ for 12 hours, the temperature was raised to 95℃, and 2 hours at 35℃.
Hold for an hour, further raise the temperature to 120℃, and hold for 3 hours at 120℃.
The polymerization was maintained for a certain period of time to complete the polymerization and obtain a vinyl polymer. 8
5℃! The polymerization rate of styrene at the second hour was 90%, which was slower than the polymerization rate in Comparative Example 3. After carrying out the same post-treatment as in Example 2, the obtained polymer has a double distribution when measured by GPGj. The top molecular weight of the peak on the polymer side was 350,000, which was lower than Comparative Example 3.

Comparative Example 3 The polymerization temperature in Example 5 was changed to 140°C, the amount of di-t-butyl peroxybenzoate was changed to 29 parts,
Polymerization was performed. The number average molecular weight (in terms of polystyrene) of the obtained polymer was 2,800. b/a is 2130
It was ha. It has an average of 0.03 main chain terminal double bonds per molecule. This polymer is used as a regulator (IV).

The same operation was performed except that the regulator (III) in Example e was changed to the regulator (mV). The polymerization rate of styrene after 12 hours at 85°C was 97%. The top molecular weight of the peak on the polymer side of the GPC chart of the obtained vinyl polymer was 5.
It was 0,000.

[Effects of the Invention] The polymerization regulator of the present invention and the vinyl polymer produced using the same have the following effects.

That is, when a polymer is manufactured using this modifier,
1. It does not become a source of bad odor from the produced polymer. Furthermore, it does not impair the heat-resistant storage stability of the produced polymer.

Furthermore, the polymerization rate can be reduced, and the heat generated by polymerization can be easily controlled.

Since the polymer obtained by the present invention exhibits the above-mentioned effects, it can be used in adhesives, paints, etc. in addition to electrophotographic toners.

-n

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, A is a styrene polymer residue, X is hydrogen, lower alkyl group, hydroxyl group, acetoxy group, lower an alkoxy group or a halogen group),
A polymerization regulator comprising a styrenic polymer having a number average molecular weight of 500 or more and having an average of 0.05 to 0.9 ethylenic double bonds per molecule at the end of the main chain. 2. The regulator according to claim 1, wherein A is a polystyrene residue. 3. A method for producing a polymer, which comprises polymerizing a vinyl monomer in the presence of the polymerization regulator according to claim 1 or 2. 4. The production method according to claim 3, wherein the polymerization is carried out by suspension polymerization. 5. The production method according to claim 3 or 4, wherein the vinyl monomer is a styrene or a monomer other than styrene. 6. The method according to any one of claims 3 to 5, wherein the polymerization is carried out in the presence of a polymerization modifier of 1 to 50% based on the weight of all monomers.