JP4465921B2 - Method for producing macromonomer - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a macromonomer that is an oligomer or polymer having a polymerizable functional group at the molecular end, and belongs to a chemical product production technique.
[0002]
[Prior art]
Macromonomer, a leading materials for multifunctional polymeric materials, various polymerizable monomer are copolymerized, Ru der what enables the production of polymers having different properties.
The polymer produced from this macromonomer is used as the main agent of paints, adhesives, molding materials, etc., or as an improving agent thereof. The paints, adhesives, molding materials, etc. are produced and used. It is widely used in various fields.
[0003]
The preparation of these macromonomers, for example, a method using a living polymerization around the ionic polymerization, Ru include chain transfer polymerization method centered radical polymerization.
In any production method, a compound having a polymerizable functional group is reacted with a functional group formed at the end of a polymer obtained by polymerizing a monomer to add a polymerizable functional group to the end of the polymer. It is a two-stage reaction.
[0004]
In contrast to such a production method, in recent years, a method of producing a macromonomer by a continuous polymerization reaction in which a monomer is reacted at a high temperature and a vinyl monomer is continuously fed into a reaction vessel for polymerization (International Patent Publication WO99 / No. 07755) has been proposed.
[0005]
A high-temperature continuous polymerization method in which a monomer is continuously supplied and polymerized is an efficient production method that can obtain a polymer in a short time (Japanese Patent Publication No. 57-502171, Japanese Patent Laid-Open No. 59-6207, No. 60-215007 and the like, and various improvements have been proposed recently (Japanese Patent Publication No. 10-511992).
[0006]
[Problems to be solved by the invention]
The inventors noticed that the production of the macromonomer by the high-temperature continuous polymerization method is a single-stage reaction compared to the conventional two-stage reaction, and is a continuous reaction, so that the production efficiency is very good. The production method of the monomer by the high-temperature continuous polymerization method was examined in search of a more efficient production method with good selectivity and yield.
[0007]
[Means for Solving the Problems]
The inventors examined various polymerization conditions in order to improve efficiency, selectivity, and yield when producing a macromonomer by a high-temperature continuous polymerization method .
As a result, when an aliphatic or alicyclic vinyl monomer is used as a monomer, and a part or all of the volatile components in the reaction liquid containing the product extracted from the reaction vessel is returned to the reaction system, The present inventors have found that a macromonomer can be produced efficiently, with good selectivity and yield, and capable of producing a macromonomer having a large number of terminal double bonds per molecule.
[0008]
That is, the invention according to claim 1 of the present invention is
While returning the volatile components in the extracted reaction liquid to the reactor,
A monomer mixture mainly composed of an aliphatic or alicyclic vinyl monomer, or an aliphatic or alicyclic vinyl monomer ,
A method for producing a macromonomer, wherein continuous polymerization is performed at a reaction temperature of 150 to 300 ° C in the presence of 0.01 to 1% by mass of a polymerization initiator based on a vinyl monomer mixture .
[0009]
The invention according to claim 2
In the manufacturing method of the macromonomer according to claim 1,
Oite the continuous polymerization,
Vinyl monomer mixture and the polymerization initiator supplied to the reaction layer, the time until recovered as reaction is characterized in that it is adjusted to 2 to 60 minutes.
[0010]
The invention according to claim 3
In the method for producing a macromonomer according to claim 1 or 2,
When using the secondary alcohol as Oite solvent to the continuous polymerization,
Its concentration is characterized in that at most 8 mass%.
[0011]
Furthermore, the invention described in claim 4
In the manufacturing method of the macromonomer in any one of Claims 1-3,
Each volatile component is
It contains a dimer of a vinyl monomer.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
<Aliphatic or alicyclic vinyl monomer>
The macromonomer produced according to the present invention is mainly composed of an aliphatic or alicyclic vinyl monomer, or a monomer mainly composed of an aliphatic or alicyclic vinyl monomer.
[0013]
Examples of the aliphatic or alicyclic vinyl monomer include monomers that are generally widely used for polymer preparation.
[0014]
Specifically, (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxy (Meth) acrylic acid hydroxyalkyl esters such as ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (meth) acrylic acid, acrylonitrile, ethylene, vinyl chloride, vinyl acetate, vinylidene chloride, etc. Can be mentioned.
[0015]
In this specification, acrylic and methacryl are collectively referred to as (meth) acryl, and acrylate and methacrylate are collectively referred to as (meth) acrylate.
[0016]
In the present invention, these aliphatic or alicyclic vinyl monomers can be used singly or as a mixture of plural vinyl monomers.
[0017]
The vinyl monomer mixture, Ru can be included a small amount of aromatic vinyl monomer.
Examples of the aromatic vinyl monomer include styrene derivatives such as styrene, vinyl toluene, α-methyl styrene, t-butyl styrene, chlorostyrene, and divinylbenzene.
[0018]
When an aromatic vinyl monomer is used in combination, the combined ratio is less than 50% by mass and preferably 15% by mass or less.
When the aromatic vinyl monomer is 50% by mass or more, that is, when the aromatic vinyl monomer is the main component, the macromonomer cannot be efficiently produced from the vinyl monomer mixture.
[0019]
<Continuous polymerization>
In the present invention, production of macromonomer, aliphatic or alicyclic vinyl monomer or a vinyl monomer mixture mainly comprising an aliphatic or alicyclic vinyl monomer, is performed by the high temperature continuous polymerization.
[0020]
As described above, the continuous polymerization and the high-temperature continuous polymerization are an efficient polymer production method (Japanese Patent Publication No. 57-502171, which can obtain a polymer in a short time by continuously supplying and polymerizing vinyl monomers as described above. JP-A-59-6207, JP-A-60-215007, etc.), but these known production methods can also be used in this invention, and among these, the preferred method for this invention is stirring. It is a continuous polymerization using a reaction vessel equipped with a machine.
[0021]
A pressure vessel is used as the reaction tank, and it is a continuous polymerization. Therefore, a stirrer with high stirring ability and stirring efficiency is used to rapidly homogenize the reaction solution and to ensure uniform heating and cooling. preferable.
[0022]
The reaction tank is heated to remove the reaction heat, and a jacket with temperature adjustment is provided so that the inside of the reaction tank can be controlled to a desired temperature. It may be provided.
[0023]
Further, the reaction vessel is provided with a supply port for a reaction raw material mixture such as a vinyl monomer and a polymerization initiator (catalyst) and a reaction solution outlet for taking out a reaction solution containing the generated reaction product (macromonomer). In order to supply the vinyl monomer and the polymerization initiator separately, a plurality of supply ports may be provided.
[0024]
The reaction tank also has a thermometer for measuring the temperature in the reaction tank, a pressure gauge for measuring the pressure in the reaction tank, a safety valve for the pressure in the reaction tank, and a nitrogen gas atmosphere in the reaction tank. Equipment required for a normal continuous reaction tank, such as a nitrogen gas supply means, is provided.
[0025]
The catalyst used in the polymerization reaction is a polymerization initiator, specifically,
Peroxides such as hydrogen peroxide, di-t-butyl peroxide, benzoyl peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2, Examples thereof include azo compounds such as 2′-azobis (2,4-dimethylvaleronitrile).
[0026]
The amount of the polymerization initiator supplied to the reaction is 0.01 to 1% by weight based on the vinyl monomer mixture supplied to the reaction .
[0027]
A solvent can be used in combination with the polymerization reaction, and aromatic hydrocarbons such as toluene and xylene, ethyl acetate, butyl acetate, cellosolve acetate, methylpropylene glycol acetate, carbitol acetate and methylpropylene glycol acetate, carbitol acetate Acetic acid esters such as ethyl carbitol acetate, ketones such as acetone and methyl ethyl ketone, alcohols such as isopropyl alcohol, ethoxyethyl propionate and the like are used.
[0028]
However, when the combination of two alcohols such as isopropyl alcohol, the concentration is used in the following 8 wt% in the reaction mixture.
If the concentration exceeds 8% by mass, the resulting macromonomer may have a small concentration of double bonds at the ends.
[0029]
The reaction temperature is a temperature 150 to 300 ° C., preferably a temperature 180 to 280 ° C., more preferably a temperature 200 to 270 ° C..
When this temperature is lower than 150 ° C., the reaction rate is slow, so that the macromonomer cannot be produced efficiently, and the viscosity of the reaction solution becomes high, and the reaction is difficult to control .
On the other hand, when the temperature exceeds 300 ° C., a decomposition reaction occurs, and the reaction product becomes low in purity or easily colored.
[0030]
When polymerizing at a temperature in the range of 150 to 300 ° C., it is possible to produce a macromonomer having a stable quality efficiently in a short time even with a small amount of polymerization initiator used, and impurities derived from the polymerization initiator In addition, a highly pure macromonomer containing almost no benzene is obtained, and the molecular weight can be adjusted by adjusting the temperature. Therefore, there is also an advantage that no chain transfer agent is required.
[0031]
The reaction time, that is, the time for the vinyl monomer mixture and the polymerization initiator to stay in the reaction tank, in other words, the time until the vinyl monomer mixture and the polymerization initiator supplied to the reaction tank are recovered as the reaction liquid is 2 to 2. It is preferably adjusted to 60 minutes and 6 to 30 minutes.
[0032]
If the residence time is less than 2 minutes, Ru Kotogaa the reaction rate of the vinyl monomers is low.
Moreover , when it exceeds 60 minutes, a macromonomer may color or productivity may fall.
[0033]
As the polymerization reaction, various methods such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization and the like can be applied, but bulk polymerization or solution polymerization using the above-described solvent is preferable because the reaction is easily controlled. is there.
[0034]
The solvent may be mixed with a vinyl monomer mixture, a polymerization initiator or the like and supplied to the reaction vessel, or may be supplied separately from them.
[0035]
When the polymerization initiator is solid, it is necessary to supply it by dissolving it in a solvent or the like, but even when it is a liquid, it is necessary to dissolve it in a solvent or the like to supply it. The amount of the solvent used is preferably in a range in which the concentration of the obtained macromonomer is 10 to 90% by mass.
[0036]
The polymerization reaction is carried out by continuously supplying the vinyl monomer mixture and the polymerization initiator together or separately to the reaction vessel, and the reaction liquid in the reaction vessel corresponding to the supply amount is continuously discharged from the outlet. The amount of the reaction solution in the reaction tank is always kept constant.
[0037]
The reaction liquid extracted from the outlet is separated into volatile components such as a macromonomer and a vinyl monomer using a thin film evaporator or the like, the macromonomer is recovered as a product, and the volatile component is returned to the reaction liquid.
[0038]
Conditions for using the thin film evaporator vary depending on the types and amounts of components to be separated, but it is usually preferable to operate at a temperature of 200 to 300 ° C. and a pressure of 0.1 to 50 kPa.
[0039]
Volatile components are separated from the macromonomer raw vinyl monomer, in addition to the solvent, Ru der those containing dimers of vinyl monomers.
The amount returned to the reaction solution is preferably 50 to 95% by mass of the separated amount, and the vinyl monomer dimer may be returned so that it is present in the reaction solution in an amount of 0.1 to 5% by mass. preferable.
The vinyl monomer dimer has a double bond and no double bond. The effect of the present invention is brought about by the vinyl monomer dimer having a double bond. It is predicted.
[0040]
The pressure during the polymerization reaction depends on the reaction temperature and the boiling point of the vinyl monomer and solvent to be used and does not affect the reaction, but may be any pressure that can maintain the reaction temperature. You may pressurize with inert gas, such as.
[0041]
The obtained macromonomer was obtained by using gel permeation chromatograph (GPC) and nuclear magnetic resonance spectrum to determine the average molecular weight and the concentration of the terminal double bond, and based on this, the terminal double contained in one macromonomer molecule. The average number of bonds was determined.
[0042]
In addition, the average value is the three types of the individual molecules produced in the present invention: those having no terminal double bond, those existing only at one end, and those existing at both ends. This is because the existence of
[0043]
As described above, by continuously polymerizing vinyl monomers, a macromonomer having a narrow molecular weight and composition distribution and a large number of terminal double bonds per molecule can be efficiently produced. It can be set as the manufacturing method of the macromonomer which improved productivity further compared with the method.
[0044]
【Example】
Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples and comparative examples.
[0045]
<Example 1>
A reaction raw material mixture having the composition shown in Table 1 was supplied at a constant rate to a stirred continuous reaction tank having a capacity of 35 liters with a jacket for heat exchange, and the reaction temperature was maintained at 270 ° C. while stirring.
After 84% of the internal volume of the reaction tank is filled with the reaction raw material, the reaction tank outlet is opened and the reaction liquid is taken out according to the supply amount of the reaction raw material mixture. The reaction was continued with the reaction material being filled.
When the supply rate of the reaction raw material mixture was maintained at 100 kg / hr, the residence time of the reaction raw material mixture in the reaction vessel was 12 minutes.
The reaction raw material mixture taken out from the reaction vessel is introduced into a thin film evaporator having a jacket heated to a temperature of 250 ° C. and having a vacuum degree of 30 kPa, and is converted into a volatile component and a polymer component containing unreacted monomers and by-products. separated.
Volatile components were recovered through a condenser, and 80% of the volatile components were fed back to the reaction tank together with the reaction raw material mixture.
[0046]
The composition of the reaction raw material mixture containing the volatile components refluxed when the steady state was reached was as follows.
In addition, the amount in parentheses is the amount of reaction raw material newly supplied.
69.10 parts by mass of butyl acrylate (59.30)
Acrylic acid 17.30 parts by mass (14.90)
Methyl ethyl ketone 3.00 parts by mass (0.67)
Vinyl dimer 0.66 parts by mass Di-t-butyl peroxide 0.03 parts by mass (0.03)
[0047]
The obtained macromonomer has a mass average molecular weight (M _W ) of 2720, a number average molecular weight (M _N ) of 1680, an acid value of 137 mgKOH / g, and the average number of terminal double bonds contained per macromonomer molecule. Was 1.03.
[0048]
[Table 1]
[0049]
In the table, BA is isobutyl acrylate, AA is acrylic acid, HA is 2-ethylhexyl acrylate, HEA is hydroxyethyl acrylate, ST is styrene, α-MeSt is α-methylstyrene, MEK is methyl ethyl ketone, and IPA is isopropyl alcohol. , DTBP is an abbreviation for di-t-butyl peroxide.
[0050]
M _W, M _N is the weight average molecular weight to number average molecular weight in terms of polystyrene measured by the above-described as gel permeation chromatography (GPC),
M _W / M _N indicates the degree of dispersion.
[0051]
Furthermore, dimer analysis of the identification manufactured by Shimadzu Corporation GCMS-QP1000, quantification was performed using a gas chromatograph.
[0052]
<Example 2>
The composition of the reaction raw material mixture was as shown in Table 1, the reaction temperature was maintained at 215 ° C., and the reaction was carried out in the same manner as in Example 1 except that 90% of the recovered volatile components were refluxed to the reactor. .
[0053]
The composition of the reaction raw material mixture containing the volatile components refluxed when the steady state was reached was as follows.
In addition, the amount in parentheses is the amount of reaction raw material newly supplied.
85.26 parts by mass of butyl acrylate (81.42)
Methyl ethyl ketone 8.53 parts by mass (1.24)
Vinyl-based dimer 0.43 parts by mass Di-t-butyl peroxide 0.08 parts by mass (0.08)
[0054]
The obtained macromonomer had a mass average molecular weight of 5660, a number average molecular weight of 2410, and an average number of terminal double bonds contained per macromonomer molecule of 0.88.
[0055]
<Example 3>
The composition of the reaction raw material mixture was as shown in Table 1, the reaction temperature was maintained at 180 ° C., 90% of the recovered volatile components were refluxed to the reactor, and the temperature of the thin film evaporator was 230 ° C. The reaction was carried out in the same manner as in Example 1 except that.
[0056]
The composition of the reaction raw material mixture containing the volatile components refluxed when the steady state was reached was as follows.
The amount in the parenthesis is the amount of the reaction raw material to be newly supplied, and the concentration of the vinyl dimer was not measured.
2-ethylhexyl acrylate 49.56 parts by mass (47.83)
Butyl acrylate 34.76 parts by mass (33.28)
3.65 parts by mass of hydroxyethyl acrylate (3.54)
8.46 parts by mass of isopropyl alcohol (1.10)
Di-t-butyl peroxide 0.08 parts by mass (0.08)
[0057]
The obtained macromonomer had a mass average molecular weight of 10430, a number average molecular weight of 3420, a hydroxyl value of 22 mgKOH / g, and an average number of terminal double bonds contained per macromonomer molecule of 0.68.
[0058]
<Comparative Example 1>
The reaction was conducted in the same manner as in Example 1 except that refluxing was not performed. The composition of the reaction raw material mixture supplied to the reactor when the steady state was reached was as follows.
79.20 parts by weight of butyl acrylate 19.80 parts by weight of acrylic acid 0.97 parts by weight of methyl ethyl ketone 0.03 parts by weight of di-t-butyl peroxide
The obtained macromonomer had a mass average molecular weight of 3600, a number average molecular weight of 1790, an acid value of 138 mg KOH / g, and an average number of terminal double bonds contained per polymer molecule of 0.84.
[0060]
<Comparative example 2>
The reaction was conducted in the same manner as in Example 2 except that refluxing was not performed. The composition of the reaction raw material mixture supplied to the reactor when the steady state was reached was as follows.
Butyl acrylate 90.83 parts by mass Methyl ethyl ketone 9.08 parts by mass Di-t-butyl peroxide 0.09 parts by mass
The obtained macromonomer had a mass average molecular weight of 5750, a number average molecular weight of 2440, and an average number of terminal double bonds contained per polymer molecule was 0.82.
[0062]
<Comparative Example 3>
A monomer mixture mainly composed of an aromatic vinyl monomer having the composition shown in Table 1 was polymerized according to Example 1.
The obtained macromonomer had a mass average molecular weight of 1470, a number average molecular weight of 690, and the average number of terminal double bonds contained per macromonomer molecule was 0.33.
[0063]
【The invention's effect】
In the present invention, an aliphatic or alicyclic vinyl monomer or a monomer mixture mainly composed of an aliphatic or alicyclic vinyl monomer is selected as a vinyl monomer constituting the skeleton of the macromonomer. When the monomer is produced, by reacting the volatile component containing the vinyl monomer dimer in the reaction solution while returning it to the reactor, the macromonomer can be produced efficiently and the productivity can be improved. In addition, there are excellent effects that the molecular weight and composition distribution of the resulting macromonomer are narrowed and that a macromonomer having a large number of terminal double bonds per molecule can be produced.

Claims (4)

While returning the volatile components in the extracted reaction liquid to the reactor,
A monomer mixture mainly composed of an aliphatic or alicyclic vinyl monomer, or an aliphatic or alicyclic vinyl monomer ,
A method for producing a macromonomer, wherein continuous polymerization is performed at a reaction temperature of 150 to 300 ° C in the presence of 0.01 to 1% by mass of a polymerization initiator based on a vinyl monomer mixture . Oite the continuous polymerization,
The method for producing a macromonomer according to claim 1, wherein the time until the vinyl monomer mixture and the polymerization initiator supplied to the reaction layer are recovered as a reaction solution is adjusted to 2 to 60 minutes. . When using the secondary alcohol as Oite solvent to the continuous polymerization,
The method for producing a macromonomer according to claim 1 or 2, wherein the concentration is 8% by mass or less. The volatile component is
The method for producing a macromonomer according to any one of claims 1 to 3, comprising a dimer of a vinyl monomer.