JPH0339528B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for producing a copolymer of p-vinylphenol and an acrylic monomer. More specifically, when copolymerizing p-vinylphenol and an acrylic monomer using a radical initiator, a copolymer of p-vinylphenol and an acrylic monomer is produced in which water coexists with phenols that do not have unsaturated side chains. Relating to a manufacturing method. Copolymers of p-vinylphenol and acrylic monomers have a variety of reactivities and high heat resistance as phenolic polymers with phenolic hydroxyl groups, as well as flexibility derived from the acrylic molecular units in the skeleton. It is attracting attention as a polymeric material that has properties not found in p-vinylphenol homopolymer, such as flexibility, adhesion, water repellency, and reactivity. be. In its various uses, molecular weights in the range of several thousand to several tens of thousands are generally desired. (Prior Art) Conventionally, regarding a method for synthesizing a copolymer of p-vinylphenol (PVP) and an acrylic monomer,
Some reports and suggestions have been made. for example,
Journal of Polymer Science A-1, No. 7
Vol., 1969, p. 2175, using azobisisobutyronitrile (AIBN) as an initiator and setting the reaction temperature to approx.
60℃ and use tetrahydrofuran as a solvent.
Synthesis method of PVP-methyl methacrylate copolymer; Journal of Polymer Science, Polymer Chemistry Edition
Chemistry Edition), Volume 13, 1975, No. 1783
The page states that AIBN is used as an initiator and the reaction temperature is 68 to 77.
A method for synthesizing PVP-fluoroalkyl methacrylate copolymers such as trifluoroethyl methacrylate and PVP-pentadecafluorooctyl acrylate copolymers at ℃; Textile and Polymer Materials Research Institute Report, No. 128, 1981 , page 66 describes a method for synthesizing a PVP-acrylonitrile copolymer using AIBN as an initiator, a reaction temperature of about 70°C, and tetrahydrofuran as a solvent; JP-A No. 58-52319,
A method for synthesizing PVP-acrylonitrile-methyl methacrylate terpolymer and PVP-methacrylonitrile-methyl acrylate terpolymer using AIBN as an initiator, a reaction temperature of about 80°C, and methyl ethyl ketone as a solvent is described. Each is listed. In these conventional methods, highly pure p-vinylphenol is used as the raw material, but the copolymerization reaction of p-vinylphenol and acrylic monomer generally has a fast reaction rate and is difficult to control. Runaway conditions tend to occur, and it is difficult to control the molecular weight of the resulting copolymer. The molecular weight of the obtained copolymer usually exceeds tens of thousands, and it is difficult to obtain with good reproducibility a copolymer having a molecular weight in the range of several thousands to tens of thousands, which is used for many purposes. Conventionally, methods using solvents have been proposed to control the copolymerization reaction, but the methods proposed so far have not yet been able to fully achieve the objective. It is difficult to produce copolymers with good reproducibility.
Note that p-vinylphenol is extremely unstable and requires complicated operations to isolate.
It is a very expensive compound. Due to these circumstances, the production of p-vinylphenol-acrylic monomer copolymers has not yet been industrialized. (Problems to be Solved) It is an object of the present invention to solve the problems of the conventional methods, and to solve p-vinylphenol-acrylic resins having a desired molecular weight within the range of several thousand to tens of thousands, for example, which has many uses. It is an object of the present invention to provide a method for copolymerizing p-vinylphenol and an acrylic monomer by which a monomer copolymer can be easily produced on an industrial scale with good reproducibility. The present invention was developed as a result of intensive studies by the inventors.
- When copolymerizing vinylphenol and acrylic monomer in the presence of a radical initiator, copolymerization is carried out in the presence of water and phenols without unsaturated side chains such as phenol, cresol, and ethylphenol in the reaction system. If the reaction is carried out, the copolymerization reaction can be appropriately suppressed without running away, and a copolymer having a desired molecular weight within the range of, for example, several thousand to tens of thousands can be easily obtained with good reproducibility; If phenols without unsaturated side chains are present in the system, the copolymerization reaction will hardly proceed at a reaction temperature of about 50 to 60°C, but if the reaction temperature is set to 70°C or higher, preferably 80°C or higher, This method was completed based on the discovery that the copolymerization reaction rapidly begins to proceed smoothly. (Means for solving the problem) Therefore, the gist of the present invention is to copolymerize p-vinylphenol and an acrylic monomer in the presence of a radical initiator. The present invention relates to a method for producing a copolymer of p-vinylphenol and an acrylic monomer, characterized in that the reaction temperature is set to 70° C. or higher in the presence of phenols and water. The reason why a copolymer having a desired molecular weight can be easily obtained with good reproducibility when according to the present invention is not clear, but the reason is that it is possible to easily obtain a copolymer having a desired molecular weight with good reproducibility. This is thought to be because undesirable runaway of the copolymerization reaction of p-vinylphenol and acrylic monomer is suppressed, and homopolymerization due to thermal polymerization of p-vinylphenol is suppressed by the water present in the reaction system. It will be done.
That is, unlike acrylic monomers, it is known that p-vinylphenol polymerizes, that is, thermally polymerizes, even in the absence of a radical initiator or a cationic initiator, and that the thermal polymerization reaction is not inhibited by radical inhibitors or the like. . Furthermore, at high temperatures of 70°C or higher, especially 80°C or higher, where the copolymerization reaction of p-vinylphenol and acrylic monomers proceeds suitably in the presence of phenols that do not have unsaturated side chains, p-vinylphenol Although homopolymerization by thermal polymerization generally occurs, it is thought that the method of the present invention suppresses the homopolymerization of p-vinylphenol that is exposed to water. The presence of water also has the side effect of allowing reaction heat to be removed by evaporation of water, making it easier to control the reaction temperature. In carrying out the present invention, one monomer, p
- As the vinylphenol, those produced by various methods can be used. For example, a method from phenol to acetoxyphenylmethyl carbinol, a method by decarboxylation of hydroxycinnamic acid, a method by decomposition of bisphenolethane,
p-vinylphenol produced by a method such as dehydrogenation of p-ethylphenol can be used. In addition, depending on the production method of these p-vinylphenols, the reaction product may contain
Phenols and/or without unsaturated side chains as unreacted raw materials, reaction diluents used, or by-products
Alternatively, water is mixed, but such mixed phenols and water can be used as phenols and water for controlling the copolymerization reaction in the present invention without separating it from p-vinylphenol unless it is particularly necessary. can. Therefore, the method of the present invention has the economical advantage that depending on the method for producing p-vinylphenol, the crude p-vinylphenol obtained during the production can be used as a copolymerization raw material without being purified. . The other acrylic monomer to be copolymerized in the present invention includes acrylic acid, methacrylic acid, esters and amides thereof, and acrylonitrile and methacrylonitrile. Examples of these esters and amides include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-acrylic acid.
-butyl, 2-ethylhexyl, stearyl, tetrahydrofuryl, cyclohexyl, benzyl,
2-hydroxyethyl, 2-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl,
2-ptoxyethyl, 2-phenoxyethyl, ethoxydiethylene glycol, phenoxydiethylene glycol, dicyclopentenyl, dicyclopentenyloxyethyl, 1-methoxycyclododecadienyl, 2,6-dibromo-4-t-butylphenyl, trifluoroethyl, Esters such as tetrafluoropropyl, octafluoropentyl, heptadecafluorodecyl; methyl, ethyl, n-propyl, i-propyl, methacrylate;
n-butyl, i-butyl, t-butyl, n-hexyl, 2-ethylhexyl, n-dodecyl, n-
Octadecyl, tetrahydrofuryl, cyclohexyl, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, polyethylene glycol, polypropylene glycol, glycerol, methoxypolyethylene glycol, 3-chloro-2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl, 3-tri Methoxysilylpropyl, 2-diphenylphosphoxyethyl, 3-
Esters such as chloro-2-acidophosphoxypropyl, trifluoroethyl, tetrafluoropropyl, octafluoropentyl, heptadecafluorodecyl; 1,4-butanediol diacrylate, pentaerythritol triacrylate,
Examples include polyfunctional acrylic esters such as trisacryloxyethyl phosphate; polyfunctional methacrylic esters such as ethylene glycol dimethacrylate and trismethacryloyloxyethylene isocyanurate; and amides such as acrylamide and methacrylamide. One type of these acrylic monomers may be used to form a binary copolymer of p-vinylphenol and one type of acrylic monomer, or two or more types may be used to form a multi-component copolymer of p-vinylphenol and two or more acrylic monomers. It is also possible to combine them. The charging ratio of p-vinylphenol and acrylic monomer used in the reaction is not particularly limited, and is based on the desired composition ratio (p
- the ratio of vinylphenol units to acrylic monomer units) and the copolymerization reaction ratio of p-vinylphenol and acrylic monomers. This charging ratio is generally selected from the range of 1:9 to 9:1, but depending on the type and use of the copolymer, the presence of very small amounts of comonomer units may result in monopolymerization. The properties may be significantly different from those of coalescence, and it is not necessarily necessary to be restricted to the above general range. Phenols without unsaturated side chains that are present in the reaction system for reaction control include phenols,
Cresol, xylenol, ethylphenol,
Examples include propylphenol and butylphenol. One type of these phenols may be used, or two or more types may be used. The amount of phenols used is generally in the range of 1 to 5000% by weight, preferably in the range of 10 to 1000% by weight, based on the total amount of p-vinylphenol and acrylic monomer. In addition, the amount of water used is generally 1 to 10% of the total amount of p-vinylphenol and acrylic monomer.
It ranges from 1000% by weight, preferably from 10 to 500% by weight. Examples of the radical initiator used in the present invention include benzoyl peroxide, acetyl peroxide, t-butyl hydroperoxide, dibenzoyl disulfide,
Examples include azobisisobutyronitrile, p-toluenesulfinic acid, ammonium persulfate, and the like.
In particular, azobisisobutyronitrile is preferably used. The appropriate amount of the radical initiator to be used is in the range of 0.1 to 10% by weight based on the entire reaction mixture (total amount of p-vinylphenol, acrylic monomer, phenols without unsaturated side chains, and water). , a range of 0.5 to 5% by weight is preferred. The radical initiator may be added to the reaction system in its entirety at once before the start of the reaction, or a portion may be added before the start of the reaction and the remaining amount may be added intermittently or continuously as the reaction progresses. It may be added at any time. In carrying out the present invention, a solvent may be used if necessary. Examples of the solvent include benzene, toluene, xylene, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, ethanol, propanol, butanol, tetrahydrofuran, dioxane, and the like. The amount of solvent to be used is not particularly limited, but is generally 0.1 based on the total amount of p-vinylphenol, acrylic monomer, and phenols without unsaturated side chains.
A range of 10 to 10 times the amount by weight is suitable. When carrying out the present invention, the reaction temperature is 70°C or higher, preferably 80°C or higher. If the reaction temperature is below 70°C, the copolymerization reaction will not proceed to achieve the desired purpose. There is no need to limit the upper limit of the reaction temperature, but it is generally up to 150°C, preferably
A temperature up to 120℃ is suitable. The copolymerization reaction is usually carried out under normal pressure, but it can also be carried out under increased pressure or reduced pressure. Further, the polymerization operation can be carried out either batchwise or continuously. The desired purpose can be achieved with a reaction time generally in the range of 10 minutes to 5 hours, preferably in the range of 30 minutes to 3 hours. After the reaction is complete, unreacted monomers and
When a phenol having no unsaturated side chain, water, or a solvent is used, the desired copolymer can be obtained by removing the solvent. The copolymer obtained by the method of the present invention usually has a linear structure with a weight average molecular weight of 2,000 to 50,000. The copolymer obtained by the method of the present invention has flexibility, adhesion, hydrophilicity, lipophilicity, water repellency, corrosion resistance, adhesiveness, antistatic property, heat resistance, etc., depending on the type of acrylic monomer used. It has various properties such as curability, UV curability, crosslinkability, flame retardancy, etc.
It also has properties derived from the p-vinylphenol used. In addition, this copolymer can be used for microphotoresists, printing PS plates, etching resists for printed wiring boards, solder resists, laminates, molding materials, paints, adhesives, inks, metal surface treatment agents, and flocculants. , antistatic agents, fiber treatment agents, etc. (Examples) The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples. Example 1 14.3 g of p-vinylphenol, 12.5 g of methyl methacrylate, 57.2 g of p-ethylphenol, 2.7 g of phenol, 12.6 g of p-cresol, 13.2 g of water, and 1.0 g of azobisisobutyronitrile (p-vinylphenol : Acrylic monomer (molar ratio)
=49:51, ratio of phenols without unsaturated side chains (total monomers (meaning the total amount of p-vinylphenol and acrylic monomer; the same applies hereinafter)) =
271% by weight, water ratio (total monomers) = 49% by weight) into an Erlenmeyer flask equipped with a cooling tube, and
Heated in an oil bath for 3 hours. After cooling the reaction product, pour it into 500ml of toluene while stirring.
Dissolve the formed precipitate in 100ml of acetone and dissolve again.
Pour into 500ml of toluene. The generated precipitate was heated to 100℃
The polymer was dried under reduced pressure to obtain 24.1 g (yield: 90% by weight) of a polymer. The weight average molecular weight of this polymer was determined to be 11,000 by gel permeation chromatography (GPC). The infrared absorption spectrum of the polymer is 3100
The absorption of OH is seen at -3700 cm ^-1 , the absorption of aromatic C=C at 1520 and 1610 cm ^-1 , the absorption of p-substituted benzene ring CH at 810 cm ^-1 , and the absorption of C=O at 1700-1720 cm ^-1 . Ta. The ¹³ C-NMR spectrum of the polymer had C absorption at the position shown by the following formula. 1: 155-157ppm, 2: 113-117ppm, 3: 128-132ppm, 4: 135-139ppm, 5: 35-50ppm, 6: 175-178ppm, 7: 49-52ppm, 8: 18-24ppm Above results The polymer was confirmed to be a copolymer of p-vinylphenol and methyl methacrylate. Moreover, m/n=56:44 (molar ratio) was calculated from the absorption intensity ratio of the ¹³ C-NMR spectrum. Example 2 A product obtained by contacting p-ethylphenol with water vapor and a dehydrogenation catalyst at high temperature (19.2% by weight of p-vinylphenol, 65.8% by weight of p-ethylphenol, 1.0% by weight of phenol, 1.5% by weight of p-cresol) reaction materials (p-vinylphenol:acrylic monomer (molar ratio) = 52:48,
The proportion of phenols without unsaturated side chains (total of monomers = 200% by weight, the proportion of water (total of monomers) = 37% by weight) was heated in a water bath at 95°C.
After continuously supplying the mixture to the reactor for 2 hours, heating was continued for 1 hour. Stirring was performed during this time. Throughout the entire period of this operation, the mixture in the reactor was maintained at a temperature below 100°C, and no reaction runaway phenomenon was observed. After the reaction is completed, the reaction product is evaporated in a thin film evaporator at 260 °C.
The copolymer was treated under conditions of 30 mmHg and 65 kg of copolymer (yield: 95%). The weight average molecular weight of the obtained copolymer was 10,500. Example 3 p-vinylphenol 115g, methacrylic acid 91g
g, p-ethylphenol 457g, phenol 17
g, p-cresol 54g, water 107g and azobisisobutyronitrile 14g (p-vinylphenol:acrylic monomer (mole ratio) = 51:49, ratio of phenols without unsaturated side chains (total monomers) ) = 256% by weight, water ratio (total monomers) = 52% by weight) was placed in an Erlenmeyer flask equipped with a stirrer and a cooling tube, and heated with stirring in a water bath at 110°C for 3 hours. After the obtained reaction product was cooled, it was poured into 10% of benzene, and the precipitate formed was
Dissolved in 500ml of methanol and poured again into 10ml of benzene. The generated precipitate was dissolved again in 500 ml of methanol, and then poured into 10 ml of water. The precipitate thus obtained was dried under reduced pressure at 60°C to give 176 g.
(Yield=85%) of the polymer was obtained. The weight average molecular weight of this polymer by GPC is
It was 13500. The infrared absorption spectrum of this polymer includes an OH absorption at 3100-3700 cm ^-1 and an OH absorption at 1700-3700 cm -1.
Absorption of C=O was observed at 1720 cm ^-1 , absorption of aromatic C=C was observed at 1520 and 1610 cm ^-1 , and absorption of p-substituted benzene ring CH was observed at 830 cm ^-1 . ¹³ C− of polymer
The NMR spectrum had C absorption at the position shown by the following formula. 1: 155-157ppm, 2: 113-117ppm, 3: 127-132ppm, 4: 135-139ppm, 5: 35-50ppm, 6: 178-182ppm, 7: 18-24ppm From the above results, the polymer is p- It was confirmed to be a copolymer of vinylphenol and methacrylic acid.
Furthermore, m/n was calculated to be 50:50 (molar ratio) from the absorption intensity ratio of the ¹³ C-NMR spectrum. Example 4 p-vinylphenol 7.7g, acrylic acid 4.2g
g, p-ethylphenol 30.3g, phenol
1.2g, p-cresol 3.6g, water 7.2g and azobisisobutyronitrile 1.0g (p-vinylphenol:acrylic monomer (molar ratio) = 52:48,
The proportion of phenols without unsaturated side chains (total of monomers = 295% by weight, the proportion of water (total of monomers) = 61% by weight) was placed in an Erlenmeyer flask equipped with a stirrer and a cooling tube, and the mixture was heated to 110% by weight. The mixture was heated in an oil bath at 0.degree. C. for 3 hours with stirring. The obtained reaction product is 1
The resulting precipitate was dissolved in 100 ml of methanol, and then poured into 1 water. The generated precipitate was dried under reduced pressure at 50°C to give 9.3g (yield = 78
%) of the polymer was obtained. The weight average molecular weight of this polymer by GPC is
It was 14,000. The infrared absorption spectrum of this polymer includes OH absorption at 3000-3700 cm ^-1 and OH absorption at 1700-3700 cm -1.
Absorption of C=O was observed at 1720 cm ^-1 , absorption of aromatic C=C was observed at 1520 and 1610 cm ^-1 , and absorption of p-substituted benzene ring CH was observed at 830 cm ^-1 . ¹³ C− of polymer
The NMR spectrum had C absorption at the position shown by the following formula. 1: 155-158ppm, 2: 114-117ppm, 3: 128-132ppm, 4: 135-139ppm, 5: 36-50ppm, 6: 177-182ppm From the above results, the polymer is composed of p-vinylphenol and acrylic acid. It was confirmed that it was a copolymer. Moreover, m/n=66:34 (molar ratio) was calculated from the absorption intensity ratio of the ¹³ C-NMR spectrum. Example 5 15.4 g of p-vinylphenol, 11.6 g of ethyl acrylate, 61.2 g of p-ethylphenol, 2.2 g of phenol, 7.2 g of p-cresol, 14.2 g of water and 1.0 g of azobisisobutyronitrile (p-vinylphenol : Acrylic monomer (molar ratio) =
52:48, ratio of phenols without unsaturated side chains (total of monomers) = 261% by weight, ratio of water (total of monomers) = 53% by weight) was placed in an Erlenmeyer flask and placed in an oil bath at 110°C. The mixture was heated with stirring for 3 hours. The obtained reaction product was poured into benzene (1), and the resulting precipitate was dissolved in 100 ml of acetone, and then poured into benzene (1). The generated precipitate
After drying at 60° C. under reduced pressure, 17.6 g (yield = 65%) of the polymer was obtained. The weight average molecular weight of this polymer by GPC is
It was 9400. The infrared absorption spectrum of this polymer includes OH absorption at 3100-3700 cm ^-1 and OH absorption at 1700-1730 cm -1.
Absorption of C=O at cm ^-1 , absorption of aromatic C=C at 1520 and 1620 cm ^-1 , p-substituted benzene ring at 830 cm ^-1
Absorption of CH was observed. The ¹³ C-NMR spectrum of the polymer had C absorption at the position shown by the following formula. 1:156-159ppm, 2:115-117ppm, 3:128-131ppm, 4:134-140ppm, 5:34-50ppm, 6:175-177ppm, 7:50-51ppm, 8:24-25ppm absorption intensity ratio m/n = 64:36 (molar ratio) was calculated. Example 6 p-vinylphenol 15.4g, acrylic acid-n
-Butyl 14.8g, p-ethylphenol 61.2g,
Phenol 2.2g, p-cresol 7.2g, water 14.2g
g and azobisisobutyronitrile 1.0 g (p
- Vinylphenol: acrylic monomer (molar ratio) = 50:50, proportion of phenols without unsaturated side chains (total of monomers) = 234% by weight, proportion of water (total of monomers) = 47% by weight) was placed in an Erlenmeyer flask and heated with stirring in a 110°C oil bath for 3 hours. After pouring the reaction product into benzene (1) and dissolving the resulting precipitate in 100ml of acetone,
Pour into benzene of 1. The obtained precipitate was dried under reduced pressure at 60°C to obtain 16.0 g (yield = 53%) of a polymer. The weight average molecular weight of this polymer by GPC was 11,200. The infrared absorption spectrum of this polymer includes an OH absorption at 3100-3700 cm ^-1 and an OH absorption at 1700 cm -1.
Absorption of C=O at -1730 cm ^-1 , 1520 and 1620 cm ^-1
An absorption of aromatic C=C was observed at 820 cm -1 and an absorption of p-substituted benzene ring CH was observed at 820 cm ^-1 . ¹³ C− of polymer
The NMR spectrum had C absorption at the position shown by the following formula. 1: 155-158ppm, 2: 115-118ppm, 3: 128-131ppm, 4: 134-140ppm, 5: 35-50ppm, 6: 175-177ppm, 7: 63-65ppm, 8: around 31ppm 9: 19- 20ppm, 10:13-14ppm From the absorption intensity ratio, m/n = 64:36 (molar ratio) was calculated. Example 7 p-vinylphenol 15.4g, acrylamide
8.2 g, p-ethylphenol 61.2 g, phenol 2.2 g, p-cresol 7.2 g, water 14.2 g, and azobisisobutyronitrile 1.0 g (p-vinylphenol: acrylic monomer (molar ratio) =
53:47, ratio of phenols without unsaturated side chains (total of monomers = 301% by weight, ratio of water (total of monomers) = 60% by weight) was placed in an Erlenmeyer flask and placed in an oil bath at 110°C. The mixture was heated with stirring for 3 hours. The reaction product was poured into 1 part of benzene, and the resulting precipitate was dissolved in 200 ml of dimethylformamide, and then poured into 1 part of benzene. The obtained precipitate was dried under reduced pressure at 80°C to obtain 14.4 g (yield = 61%) of a polymer. This polymer was insoluble in acetone and water, but soluble in a water-methanol mixed solvent.
Homopolymers of p-vinylphenol are soluble in acetone, while homopolymers of acrylamide are soluble in water. Therefore, based on its solubility, this polymer was recognized as a copolymer rather than a mixture of p-vinylphenol and acrylamide homopolymers. The infrared absorption spectrum of the polymer includes OH absorption at 3000-3700 cm ^-1 , amide C=O absorption at 1660 cm ^-1 , aromatic C=C absorption at 1520 and 1610 cm ^-1 , and p at 830 cm ^-1 . -Substituted benzene ring CH
absorption was observed. The ¹³ C-NMR spectrum of the polymer had C absorption at the position shown by the following formula. 1:155-158ppm, 2:115-118ppm, 3:129-132ppm, 4:134-139ppm, 5:37-50ppm, 6:180-184ppm m/n = 56:44 (molar ratio) from absorption intensity ratio It was calculated that Example 8 7.2 g of p-vinylphenol, 3.2 g of acrylonitrile, 31.1 g of p-ethylphenol, 1.0 g of phenol, 3.2 g of p-cresol, 7.5 g of water, and 1.0 g of azobisisobutyronitrile (p-vinylphenol: acrylic System monomer (molar ratio) =
50:50, ratio of phenols without unsaturated side chains (total of monomers) = 339% by weight, ratio of water (total of monomers) = 72% by weight) was placed in an Erlenmeyer flask and placed in an oil bath at 110°C. The mixture was heated with stirring for 3 hours. Pour the reaction product into 1 part of toluene, dissolve the resulting precipitate in 100 ml of acetone, and then add 1 part toluene.
of toluene. The obtained precipitate was dried under reduced pressure at 60°C to obtain 9.5 g (yield = 91%) of a polymer. The weight average molecular weight of this polymer by GPC is
It was 12500. The infrared absorption spectrum of this polymer includes OH absorption at 3100-3700 cm ^-1 and 2240 cm ^-1
absorption of C≡N, aromatic C at 1520 and 1610 cm ^-1
It had an absorption of =C and an absorption of p-substituted benzene ring CH at 830 cm ^-1 . The ¹³ C-NMR spectrum of the polymer had C absorption at the position shown by the following formula. 1:156-159ppm, 2:114-117ppm, 3:128-132ppm, 4:132-137ppm, 5:36-50ppm, 6:121-124ppm m/n = 56:44 (molar ratio) from absorption intensity ratio It was calculated that Example 9 150g p-vinylphenol, methacrylic acid-
2-hydroxyethyl 160g, p-ethylphenol 416g, phenol 7g, p-cresol 22
g, water 105 g, and azobisisobutyronitrile 14 g (p-vinylphenol:acrylic monomer (monomer ratio) = 50:50, ratio of phenols without unsaturated side chains (total monomer) = 144 weight %, the proportion of water (total monomers) = 34% by weight),
The mixture was placed in a flask equipped with a stirrer and a condenser, and heated and stirred in a 90°C oil bath for 2 hours. The reaction product was poured into 10 parts of toluene, and the resulting precipitate was dissolved in 1 part of acetone, and then poured into 10 parts of toluene. The obtained precipitate was dried under reduced pressure at 60°C to give 270g (yield 87%).
A polymer was obtained. The weight average molecular weight of this polymer by GPC is
It was 11000. The infrared absorption spectrum of this polymer includes OH absorption at 3000-3700 cm ^-1 and OH absorption at 1700-3700 cm -1.
Absorption of C=O at 1730 cm ^-1 , absorption of aromatic C=C at 1520 and 1620 cm ^-1 , absorption of primary alcohol C-O at 1080 cm ^-1 , p-substituted benzene ring CH at 830 cm ^-1
It had an absorption of The ¹³ C-NMR spectrum of the polymer had C absorption at the position shown by the following formula. 1: 155-157ppm, 2: 114-117ppm, 3: 128-132ppm, 4: 134-139ppm, 5: 37-53ppm, 6: 176-178ppm, 7: 66-68ppm, 8: 60-61ppm, 9: From the absorption intensity ratio of 20-21 ppm, m/n was calculated to be 57:43 (molar ratio). Example 10 p-vinylphenol 15.5g, acrylic acid-2
-Hydroxyethyl 15.0g, p-ethylphenol 65.6g, phenol 2.0g, p-cresol 5.5
g, water 11.4 g and azobisisobutyronitrile
2.0g (p-vinylphenol: acrylic monomer (molar ratio) = 50:50, proportion of phenols without unsaturated side chains (total of monomers) = 240% by weight, proportion of water (total of monomers) = 37% by weight),
The mixture was placed in an Erlenmeyer flask and heated in a 100°C oil bath for 2 hours with stirring. The reaction product was poured into 700 ml of toluene, and the resulting precipitate was dissolved in 100 ml of acetone, and then poured into 700 ml of toluene. The obtained precipitate was dried under reduced pressure at 60° C. to obtain 27.0 g (yield: 89%) of a polymer. The weight average molecular weight of this polymer by GPC is
It was 10,700. The infrared absorption spectrum of this polymer includes an OH absorption at 3000-3700 cm ^-1 and an OH absorption at 1710-3700 cm -1.
Absorption of C=O at 1730 cm ^-1 , absorption of aromatic C=C at 1520 and 1620 cm ^-1 , absorption of primary alcohol C-O at 1080 cm ^-1 , p-substituted benzene ring CH at 830 cm ^-1
absorption was observed. The ¹³ C-NMR spectrum of the polymer had C absorption at the position shown by the following formula. Absorption intensity From the ratio, it was calculated that m/n = 56:44 (molar ratio). Example 11 5.8 g p-vinylphenol, 10.2 g benzyl methacrylate, 30.4 g p-ethylphenol, 1.4 g phenol, 6.1 g p-cresol, 6.3 g water and 1.0 g azobisisobutyronitrile (p-vinylphenol : Acrylic monomer (molar ratio)
= 45:55, ratio of phenols without unsaturated side chains (total of monomers) = 237% by weight, ratio of water (total of monomers) = 39% by weight) was placed in an Erlenmeyer flask and heated in an oil bath at 110°C. The mixture was heated for 3 hours with stirring. Pour the reaction product into 1 part of toluene, dissolve the resulting precipitate in 100 ml of acetone, and then add 1 part toluene.
of toluene. The obtained precipitate was dried under reduced pressure at 60°C to obtain 11.0 g (yield = 69%) of a polymer. The weight average molecular weight of the polymer by GPC was 11,000. The infrared absorption spectrum of the polymer contains 3100
Absorption of OH at −3700 cm ⁻¹ , C= at 1700−1730 cm ⁻¹
absorption of O, absorption of aromatic C=C at 1520 and 1620 cm ^-1 , absorption of p-substituted benzene ring CH at 820 cm ^-1 ,
Absorption of monosubstituted benzene ring CH was observed at 690 and 730 cm ^-1 . The ¹³ C-NMR spectrum of the polymer showed absorption at C at the position shown by the following formula. 1: 155-157ppm, 2: 114-116ppm, 3: 128-131ppm, 4: 135-139ppm, 5: 35-55ppm, 6: 175-177ppm, 7: 75-77ppm m/n = 47 from absorption intensity ratio :53 (molar ratio). Example 12 5.8 g of p-vinylphenol, 3.0 g of vinyl methacrylate, 30.4 g of p-ethylphenol, p-
6.1 g of cresol, 6.3 g of water, and 1.0 g of azobisisobutyronitrile (p-vinylphenol:acrylic monomer (mole ratio) = 62:38, ratio of phenols without unsaturated side chains (total monomers) =415% by weight, proportion of water (total monomers) =
(72% by weight) was placed in an Erlenmeyer flask and heated with stirring in a 110°C oil bath for 3 hours. The reaction product was poured into 1 part of toluene, and the resulting precipitate was dissolved in 100 ml of acetone, and then poured into 1 part of toluene. The obtained precipitate was dried under reduced pressure at 60℃, and 6.1g
(Yield=69%) of the polymer was obtained. The weight average molecular weight of this polymer by GPC is
It was 7400. The infrared absorption spectrum of this polymer includes OH absorption at 3100-3700 cm ^-1 and OH absorption at 1720-1740 cm -1.
The absorption of C=O at cm ^-1 , the absorption of -CH=CH ₂ at 1650 cm ^-1 , the absorption of aromatic C=C at 1520 and 1610 cm ^-1 , and the absorption of p-substituted benzene ring CH at 830 cm ^-1 are observed. It was done. The ¹³ C-NMR spectrum of the polymer showed absorption at C at the position shown by the following formula. 1: 155-157ppm, 2: 115-117ppm, 3: 128-131ppm, 4: 135-137ppm, 5: 38-52ppm, 6: 172-175ppm, 7: 141-143ppm, 8: 96-98ppm, 9: 19-22ppm The obtained product is a copolymer represented by the above formula, and p-vinylphenol and

The fact that it is not a copolymer with [formula] means that if ₁₀ C is present, ¹³ C-NMR
Although the absorption (approximately 136 ppm) should be observed in the spectrum, it is clear that no such absorption is observed. m/n=57:43 (molar ratio) was calculated from the absorption intensity ratio. Example 13 5.8 g of p-vinylphenol, 2 acrylic acid,
2,3,3-tetrafluoropropyl 9.6 g, phenol 1.4 g, p-cresol 6.1 g, water 6.3 g and azobisisobutyronitrile 1.0 g (p-vinylphenol: acrylic monomer (molar ratio)
= 46:54, proportion of phenols without unsaturated side chains (total of monomers) = 49% by weight, proportion of water (total of monomers) = 41% by weight) were placed in an Erlenmeyer flask and heated in an oil bath at 110°C. The mixture was heated for 3 hours with stirring. Pour the reaction product into 1 hexane, dissolve the resulting precipitate in 100 ml of acetone, and then add 1
of hexane. The obtained precipitate was dried under reduced pressure at 60°C to obtain 8.4 g (yield = 55%) of a polymer. The weight average molecular weight of this polymer by GPC is
It was 7400. Further, the fluorine content measured by the Uyck-Bold method was 12.9% by weight. The infrared absorption spectrum of the polymer includes 3100−3700 cm ^-1
OH absorption at 1750 cm ^-1 , C=O absorption at 1750 cm -1, aromatic C=C absorption at 1520 and 1610 cm ^-1 , C-F absorption at 1100 cm ^-1 , p-substituted benzene ring CH at 830 cm ^-1
absorption was observed. The ¹³ C-NMR spectrum of the polymer showed absorption at C at the position shown by the following formula. Absorption intensity ratio It was calculated that m/n=73:27 (molar ratio). Example 14 5.8g p-vinylphenol, methacrylic acid-
9.1 g of 2-dimethylaminoethyl, 30.4 g of p-ethylphenol, 1.4 g of phenol, 6.1 g of p-cresol, 6.3 g of water, and 1.0 g of azobisisobutyronitrile (p-vinylphenol: acrylic monomer (molar ratio)) = 45:55, ratio of phenols without unsaturated side chains (total monomers) =
254% by weight, water ratio (total monomers) = 42% by weight) was placed in an Erlenmeyer flask and heated in an oil bath at 110℃ for 2 hours.
Heat with stirring for an hour. The reaction product was poured into 1 part of n-hexane, and the resulting precipitate was poured into 1 part of n-hexane.
After washing twice with hexane, it was dissolved in 100 ml of acetone and poured into 1 part of toluene. The obtained precipitate was dried under reduced pressure at 60°C to obtain 8.0 g (yield = 54%) of a polymer. This polymer was soluble in dilute hydrochloric acid. This indicates that the product does not contain a homopolymer of p-vinylphenol. The nitrogen content measured by chemiluminescence method was 4.1% by weight. The infrared absorption spectrum of the polymer contains 3000−
OH absorption at 3700cm ^-1 , C=O absorption at 1730cm ^-1 ,
Absorption of aromatic C=C at 1520 and 1620 cm ^-1 , 830
Absorption of p-substituted benzene ring CH was observed at cm ^-1 .
The ¹³ C-NMR spectrum of the polymer showed absorption at C at the position shown by the following formula. 1: 155-158ppm, 2: 114-116ppm, 3: 127-131ppm, 4: 135-139ppm, 5: 35-55ppm, 6: 174-177ppm, 7: 60-64ppm, 8: 56-59ppm, 9: From the absorption intensity ratio of 17-23ppm and 10:44-47ppm, it was calculated that m/n = 55:45 (molar ratio). Example 15 5.8 g of p-vinylphenol, methacrylic acid
3-trimethoxysilylpropyl 7.4g, p-ethylphenol 30.4g, phenol 1.4g, p-
6.1 g of cresol, 6.3 g of water, and 1.0 g of azobisisobutyronitrile (p-vinylphenol:acrylic monomer (mole ratio) = 62:38, ratio of phenols without unsaturated side chains (total monomers) =287% by weight, proportion of water (total monomers) =
(48% by weight) was placed in an Erlenmeyer flask and heated in a 110°C oil bath for 2 hours with stirring. The reaction product was poured into 1 part of toluene, and the resulting precipitate was dissolved in 100 ml of acetone, and then poured into 1 part of toluene. The obtained precipitate will gel and become insoluble in the solvent even if it is dried at room temperature, so it should be dried in a state containing toluene.
GPC and ¹³ C-NMR were measured. The yield on a dry matter basis was 79%. Further, the silica content measured by W-ICP method was 5.9% by weight. G.P.C.
The weight average molecular weight was 68,000. The infrared absorption spectrum includes OH absorption at 3100-3700 cm ^-1 , C=O absorption at 1700-1730 cm ^-1 , 1520 and
Absorption of aromatic C=C at 1620 cm ^-1 and at 1080 cm ^-1
Absorption of SiOC, p-substituted benzene ring CH at 820 cm ^-1
absorption was observed. The ¹³ C-NMR spectrum showed absorption at the position shown by the following formula. 1: 155-158ppm, 2: 114-117ppm, 3: 128-131ppm, 4: 135-139ppm, 5: 35-55ppm, 6: 175-178ppm, 7: 66-68ppm, 8: 49-51ppm, 9. From the absorption intensity ratios of 11:18-24ppm and 10:5-7ppm, m/n was calculated to be 62:38 (molar ratio). Example 16 p-vinylphenol 14.3g, methyl methacrylate 12.6g, p-ethylphenol 157.2g, phenol 2.7g, p-cresol 12.6g, water 13.2g
and 2.0 g of azobisisobutyronitrile (p-
Vinyl phenol: acrylic monomer (mole ratio) = 50:50, proportion of phenols without unsaturated side chains (total of monomers) = 641% by weight, proportion of water (total of monomers) = 49% by weight) The mixture was placed in an Erlenmeyer flask and heated in an oil bath at 110°C for 3 hours with stirring. After cooling the reaction product, pour it into 1 part of toluene with stirring, and add 100 parts of the precipitate to 1 part of toluene with stirring.
ml of acetone and poured again into 500 ml of toluene. The obtained precipitate was dried under reduced pressure at 100℃,
17.4 g (yield = 66%) of polymer was obtained. The weight average molecular weight of this polymer by GPC is
It was 5700. Furthermore, from the absorption intensity ratio of the ¹³ C-NMR spectrum of the polymer, p-vinylphenol unit/methyl methacrylate unit =
It was calculated to be 55:45 (molar ratio). Example 17 14.3 g p-vinylphenol, 22.3 g methyl methacrylate, 57.2 g p-ethylphenol, 2.7 g phenol, 12.6 g p-cresol, 13.2 g water and 1.1 g azobisisobutyronitrile (p-vinylphenol : Acrylic monomer (molar ratio)
= 35:65, ratio of phenols without unsaturated side chains (total of monomers) = 198% by weight, ratio of water (total of monomers) = 36% by weight) was placed in an Erlenmeyer flask and heated in an oil bath at 85°C. The mixture was heated for 3 hours with stirring. After cooling the reaction product, 1
The resulting precipitate was dissolved in 100 ml of acetone and poured into 500 ml of toluene again.
The obtained precipitate was dried under reduced pressure at 100℃, and 25.9g
(Yield=71%) of the polymer was obtained. The weight average molecular weight of this polymer by GPC is
It was 30500. Also, from the absorption intensity ratio of the ¹³ C-NMR spectrum of the polymer, p-vinylphenol unit/methyl methacrylate unit =
It was calculated to be 42:58 (molar ratio). Example 18 14.3 g of p-vinylphenol, 3.0 g of methyl methacrylate, 57.2 g of p-ethylphenol, 2.7 g of phenol, 12.6 g of p-cresol, 13.2 g of water,
and 0.9 g of azobisisobutyronitrile (p-
Vinyl phenol: acrylic monomer (mole ratio) = 81:19, proportion of phenols without unsaturated side chains (total of monomers) = 419% by weight, proportion of water (total of monomers) = 76% by weight) The mixture was placed in an Erlenmeyer flask and heated in an 85°C oil bath for 4 hours with stirring. After cooling the reaction product, pour it into 1 toluene with stirring, and add 100ml of the precipitate formed.
of acetone and poured again into 500 ml of toluene. The obtained precipitate was dried under reduced pressure at 100℃, and 6.1
g (yield=35%) of polymer was obtained. The weight average molecular weight of this polymer by GPC is
It was 7300. Furthermore, from the absorption intensity ratio of the ¹³ C-NMR spectrum of the polymer, p-vinylphenol and
Unit/methyl methacrylate unit = 81:
It was calculated to be 19 (molar ratio). Example 19 14.3 g p-vinylphenol, 12.0 g methyl methacrylate, 5.7 g p-ethylphenol, 0.3 g phenol, 1.3 g p-cresol, 6.6 g water, 30 g tetrahydrofuran, and 1.0 g azobisisobutyronitrile (p - Vinylphenol: Acrylic monomer (mole ratio) = 50:50, ratio of phenols without unsaturated side chains (total monomers)
= 29% by weight, water ratio (total monomers) = 25% by weight) was placed in an Erlenmeyer flask and heated with stirring in an oil bath at 110°C for 3 hours. After cooling the reaction product, pour it into 500ml of toluene while stirring.
Dissolve the formed precipitate in 100ml of acetone and dissolve again.
Pour into 500ml of toluene. The obtained precipitate was heated to 100℃
The polymer was dried under reduced pressure to obtain 22.5 g (yield: 86%) of a polymer. The weight average molecular weight of this polymer by GPC was 38,000. Comparative Example 1 14.3 g of p-vinylphenol, 12.0 g of methyl methacrylate, 30 g of tetrahydrofuran, and 0.5 g of azobisisobutyronitrile (p-vinylphenol:acrylic monomer (molar ratio) = 50:50)
was placed in an Erlenmeyer flask and heated with stirring in a 70°C oil bath for 4 hours. The reaction product was poured into 500 ml of toluene, and the resulting precipitate was dissolved in 100 ml of acetone and poured again into 500 ml of toluene. The obtained precipitate was dried under reduced pressure at 100°C to give 22.3g (yield =
85%) of the polymer was obtained. The weight average molecular weight of this polymer by GPC is
It was 147,000.

Claims (1)

[Claims] 1. When copolymerizing p-vinylphenol and an acrylic monomer in the presence of a radical initiator, a phenol having no unsaturated side chain and water are present in the reaction system, and the reaction temperature is lowered. 1. A method for producing a copolymer of p-vinylphenol and an acrylic monomer, characterized in that the temperature is 70°C or higher. 2. The method according to claim 1, wherein the amount of the phenol having no unsaturated side chain is 1 to 5000% by weight based on the total amount of p-vinylphenol and acrylic monomer. 3 The amount of water present is 1 to 1000% by weight based on the total amount of p-vinylphenol and acrylic monomer.
The method according to claim 1.