JPH03111412A - Preparation of graft copolymer - Google Patents

Abstract

PURPOSE:To improve the polarity, hydrogen bonding ability, heat resistance, and alkali solubility by reacting a specific polymer with a p-vinylphenol of which the hydroxyl group may be protected by an easily eliminatable protective group. CONSTITUTION:p-Vinylphenol of which the hydroxyl group may be protected by an easily eliminatable protective group is reacted with a polymer having a wt.-average mol.wt. of 1000-10000 and (meth)acryloyl groups at the molecular terminals and consisting of a monomer other than vinylphenol [e.g. a polystyrene having (meth)acryloyl groups at the molecular terminals] in the presence of a radical initiator (e.g. azobisisobutyronitrile) in an amt. of 0.01-10wt.% based on the reaction mixture at 30-150 deg.C for 30min to 3hr to give a graft copolymer in which a unit of formula I (wherein X is H or a protective group) and a unit of formula II [wherein R is methyl or H; and Y is a residue of the (meth) acryloyl group-contg. polymer from which (meth)acryloyl groups have been removed] are randomly linked and which has a wt.-average mol.wt. of 5000-100000.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing a graft copolymer, and more specifically, to a method for producing a graft copolymer, and more specifically, it relates to a method for producing a graft copolymer. Protected p-vinylphenol and a polymer having a methacryloyl group at the end and having a monomer other than vinylphenol as a constituent, and/or a polymer having an acryloyl group at the end and having a monomer other than vinylphenol as a constituent. From, p
- A method for producing a graft copolymer in which a polymer containing a monomer other than vinylphenol as a side chain is grafted onto a backbone polymer containing vinylphenol as a main constituent.

(Prior Art) Poly-p-vinylphenol has been known as a polymer with phenolic hydroxyl groups, and has various reactivities and high heat resistance, so it is used in thermosetting resins, photosensitive materials, and rust preventive agents. It is widely used in various fields such as ℃・. As a manufacturing method, p-vinylphenol is radically polymerized using, for example, azobisisobutyronitrile as an initiator (Journal of Organic
Chemistry.

24, 1345 (1959)) or, for example, a method of cationic polymerization using boron trifluoride diethyl ether as an initiator (Journa, l of Polyme
rScience, A-1, Volume 7, 2405 (19
69)) etc. are not known.

By the way, attempts have been made to synthesize various copolymers in order to impart other properties to IJ-p-vinylphenol, which has the above-mentioned excellent properties. For example, copolymers of p-vinylphenol and methyl methacrylate or styrene (Journal of Polymer 5c
ience, A-1, vol. 7, 2175 (1969))
, a copolymer of p-vinylphenol and butyl acrylate (JP-A-61-291606), and the like are known. The properties of these random or alternating copolymers are
It is an average or intermediate between the respective homopolymers of p-vinylphenol and comonomer, and while new properties are added by introducing the comonomer, the IJ-p
- There is no tendency for the properties of vinylphenol to become diluted.

Generally, it is known that a block or graft copolymer is produced as a method for imparting new properties of a polymer while sufficiently retaining the properties of a certain polymer.

Regarding block copolymers of p-vinylphenol,
p-vinylphenol produced by a method in which 4-(tert-butyldimethylsilyl)ether of p-vinylphenol and styrene are subjected to living polymerization in the presence of lithium natutalide, and then the tert-butyldimethylsilyl group is eliminated. and styrene block copolymer (JP-A-59-53516
Publication No.) is known. In addition, regarding the graft copolymer of p-vinylphenol, after irradiating polyethylene with ionizing radiation, p-acetoxystyrene is applied to graft polymerize it, and then the acetyl group is eliminated. Graft copolymers (JP-A-50-78690), in which side chains containing p-vinylphenol as a constituent are grafted thereto, are known. However, a method for producing a graft copolymer having poly-p-vinylphenol as a backbone and having another polymer as a side chain is not yet known, and such a graft copolymer has not yet been provided.

(Problems to be Solved by the Invention) In view of the above situation, an object of the present invention is to
The purpose of this invention is to develop a method for producing a graft copolymer having vinylphenol as a backbone and other polymers as side chains, thereby providing a graft copolymer with excellent properties.

(Means for Solving the Problem) The present inventor conducted extensive research to achieve the above object, and found that in the presence of a radical initiator, p-vinylphenol, p-vinylphenol,
and reacting a polymer having a methacryloyl group or an acryloyl group at the end and having a monomer other than vinylphenol as a constituent.Thus, by reacting a polymer having a monomer other than vinylphenol as a constituent with a base polymer containing p-vinylphenol as a main constituent, A graft copolymer is produced in which a polymer having K as a side chain is grafted. When used, a similar graft copolymer having p-vinylphenol whose hydroxyl group is protected with a protecting group as the main component of the backbone polymer is produced, and when the protecting group is removed from the graft copolymer, The present invention was completed by discovering that a graft copolymer of a backbone polymer containing p-vinylphenol as a main component can be obtained.

That is, the gist of the present invention is to provide p-vinylphenol whose hydroxyl group may or may not be protected with an easily removable protecting group, and a polymer having a methacryloyl group at the terminal and containing a monomer other than vinylphenol as a constituent component. and/
Alternatively, the present invention resides in a method for producing a graft copolymer, which comprises reacting a polymer having an acryloyl group at the end and having a monomer other than vinylphenol as a constituent in the presence of a radical initiator.

The p-vinylphenol used as a reaction raw material in the present invention can be produced by various methods. For example, a method obtained from phenol via acetoxyphenylmethyl carbinol, a method by decarboxylation of hydroxycinnamic acid, a method by decomposition of bisphenol ethane, p.
- Those produced by a method such as dehydrogenation of ethylphenol can be used. Also, these p-
Depending on the method for producing vinylphenol, unreacted raw materials, diluents, or byproducts such as p-ethylphenol, cresol, and other phenols that do not have unsaturated side chains and water may coexist in the reaction product. Phenols and arsenic water that do not have saturated side chains can be used as a reaction trap for crude p-vinylphenol containing them without being separated from p-vinylphenol. Using such crude p-vinylphenol as a reaction raw material is economical because the cost for purifying p-vinylphenol can be reduced.

In addition, p whose hydroxyl group is protected with an easily removable protecting group can also be used.
- Vinylphenol may also be used. In this case, protecting groups that are easily removed include alkyl groups such as methyl group and tert-butyl group, acyl group such as formyl group and acetyl group, tert-butoxycarbonyl group, and isopropoxycarbonyl group. Examples include alkyloxycarbonyl groups and alkylsilyl groups such as trimethylsilyl groups.

Next, the polymer having a methacryloyl group or an acryloyl group at the terminal, which is the other reaction raw material in the present invention, will be explained. The polymer is selected from polymers containing a monomer other than vinylphenol and having a methacryloyl group or an acryloyl group bonded to the terminal end of the polymer. The polymer ideally has an extremely narrow monodisperse molecular weight distribution, but in practice it is suitably a polymerizable polymer called a macromer, which has a relatively narrow degree of dispersion. .

The general method for producing this polymer is to first polymerize monomers by a method that allows the molecular weight distribution to be controlled to a narrow degree of dispersion, and then to bond a methacryloyl group or acryloyl group to one end of the monomer. It is. As a polymerization method for monomers that can control molecular weight distribution, in general, for monomers that can undergo ping anionic polymerization such as styrene, isoprene, and butadiene,
Living anionic polymerization is performed using an alkali alkali metal such as butyl lithium as an initiator, and monomers capable of radical polymerization such as methyl methacrylate and ethyl acrylate are polymerized in the presence of a chain transfer agent such as thioglycolic acid. Radical polymerization is carried out using azobisisobutyronitrile or the like as an initiator. In addition, for cationically polymerizable imbutylene, an inifer polymerization method is applied that uses RCA (R means an alkyl group) and BC43, which function as an initiator and a chain transfer agent, and ethyl vinyl ether A living cationic polymerization method using , HI and Technique 2 is applied.

Additionally, the monomers constituting the polymer are not limited to vinyl polymerizable monomers, but include, for example, ethylene oxide,
It may be an open polymerizable polymer such as tetrahydrofuran. Usually, for ethylene oxide, a ring-opening polymerization method using potassium p-impropenylbenzyl oxide is applied, and for tetrahydrofuran, a ring-opening polymerization method using Et30BF4 is applied. be done. The method of bonding a methacryloyl group or an acryloyl group to the terminal end of a polymer prepared by regulating the molecular weight distribution by the above polymerization method is selected as appropriate depending on the terminal structure of the polymer at the time the polymerization is completed. For example, in the case of an alkaline earth polymer whose terminal end is bonded to an alkyl group, a method is adopted in which the polymer is reacted with ethylene oxide to form a metal alkoxide and then reacted with methacryloyl chloride or acryloyl chloride.
When the polymer terminal has a thioglycolic acid structure, a method of reacting glycidyl methacrylate or glycidyl acrylate is employed.

The polymer is generally prepared by regulating the molecular weight distribution as described above, but the molecular weight itself does not need to be particularly limited and is appropriately selected as necessary. Usually, those having a weight average molecular weight in the range of 1,000 to 10,000 are preferred. Examples of such polymers include polystyrene, polybutadiene, polyisoprene, polyisobutylene, polyethylene oxide, polytetrahydrofuran, polyvinyl ether, styrene-acrylolitrile copolymer, polymethyl methacrylate, and polyacrylic acid having a methacryloyl group or acryloyl group at the end. Examples include ethyl, polybutyl acrylate, and polydimethylsiloxane. Two or more of these may be used in combination if necessary.

In carrying out the present invention, the above-mentioned p-vinylphenol or p-vinylphenol whose hydroxyl group is protected with a protecting group (hereinafter both are abbreviated as "Itp VP etc."), the above-mentioned polymer having a methacryloyl group and/or or a polymer having an acryloyl group (hereinafter both are referred to as 1)
1 methacryloyl group, etc.)
is reacted in the presence of a radical initiator. Examples of such radical initiators include benzoyl peroxide, acetyl peroxide, tert-butyl hydroperoxide, dibenzoyl disulfide, azobisine butyronitrile, p
Examples include -toluenesulfinic acid, ammonium peroxide, etc., and azobisisobutylonitrile is particularly preferred. The amount of radical initiator to be used is 0.000% relative to the reaction mixture.
A range of 0.01 to 10% by weight is appropriate, and 0.1 to 5% by weight.
Weight/weight scales are preferred. The radical initiator may be added to the reaction system in a predetermined amount all at once, or may be added intermittently or continuously as the reaction progresses.

Moreover, a solvent can be used as necessary in the reaction. Examples of the solvent include benzene, toluene, xylene, acetone, methyl ethyl ketone, ethyl acetate, methanol, ethanol, propatool, tetrahydrofuran, dioxane, etc., and mixtures thereof, and the amount used is arbitrary. Reaction temperature is 30 to 150 tl
A range of :' is appropriate, and a range of 60 to 110C is preferable. The reaction time is suitably in the range of 5 minutes to 5 hours,
A range of 30 minutes to 3 hours is preferred. The reaction pressure may normally be normal pressure, but the reaction can also be carried out under increased pressure or reduced pressure if necessary. However, the reaction operation can be carried out either batchwise or continuously.

In carrying out the present invention, the reaction raw materials p-VP, etc. and the polymer having methacryloyl groups, etc. can be used in any ratio, but generally the ratio of p-VP, etc./polymer having methacryloyl groups, etc. In terms of molar ratio, however, for polymers having methacryloyl groups, etc., the repeating units constituting the polymer are taken as 1 mole, and the ratio is 20/80 to 20/80.
A range of 80/20 is appropriate. When this ratio is large (a large amount of p-VP, etc.), the reaction rate of polymers having methacryloyl groups etc. generally improves, but on the other hand, the amount of produced homopolymers such as p-VP that are not grafted increases.

In the reaction according to the present invention, unlike the usual copolymerization reaction between low molecular weight monomers, a homopolymer such as pvP is also produced, and unreacted p-VP is extracted from the obtained reaction product.
The so-called gross polymer, which excludes low-molecular compounds such as etc. and the solvent used, usually contains the target product, a graft copolymer and a homopolymer such as pvP, and in some cases, methacryloyl A/ It also includes polymers having groups, etc., and may be composed of these three types of polymers. In order to isolate the graft copolymer which is the target product of this gross polymer, any method such as a solvent extraction method using a combination of solvents with different solubility for the constituent polymers or a fractional precipitation method can be applied. . Of course, in some cases, the target graft copolymer may be used as it is without isolating the graft copolymer.

The graft copolymer obtained in the present invention is generally a polymer having a unit represented by the following formula (I) based on p-VP etc. used as a reaction raw material and a methacryloyl group etc. used as the other reaction raw material. Based on the following formula (II)
When the units shown by are randomly combined, p
-A backbone polymer whose main component is vinylphenol,
It is a graft copolymer in which a polymer containing a monomer other than vinylphenol is grafted as a side chain.

[In the formula, X is hydrogen or a protecting group. [In the formula, R is a methyl group or hydrogen, and Y is the remainder of a polymer having a methacryloyl group, etc., after removing the methacryloyl group (R=methyl group) or acryloyl group (R=hydrogen).

] The molecular weight of this graft copolymer can vary depending on the reaction conditions employed or the molecular weight of the polymer having methacryloyl groups etc. used as a reaction raw material. can be selected according to
Although not particularly limited, the weight average molecular weight is usually about 5,000 to 100,000.

In addition, a graft copolymer in which X in the unit of formula (1) is a protecting group, that is, a graft copolymer obtained by using p-vinylphenol whose hydroxyl group is protected with an easily removable protecting group as a reaction raw material. The protective group of the polymer can be easily removed by physical or chemical treatment such as heating or hydrolysis treatment, and the polymer can be easily converted into a graft copolymer in which X in the unit of formula (I) is hydrogen. be able to.

(Effects of the Invention) According to the present invention, various graft copolymers are produced in which various polymers prepared from various polymerizable monomers are grafted as side chains to a backbone polymer containing p-vinylphenol as a main component. % can be easily calculated. The graft copolymer containing p-vinylphenol as the main component of the backbone polymer obtained by the present invention has the characteristics of poly-p-vinylphenol such as polarity, hydrogen bonding property, heat resistance, alkali solubility, chemical Conventionally, it has excellent properties such as reactivity, and in addition, depending on the type of side chain polymer grafted, it also has other properties such as lipophilicity or hydrophilicity, rigidity or flexibility. It has many uses in plastic surface modifiers, plastic compatibilizers, paints, adhesives, pressure-sensitive adhesives, molding materials, laminated materials, films, etc.

(Examples) The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples.

Example 1 Crude p-vinylphenol obtained by dehydrogenating p-ethylphenol (p-vinylphenol 2
z, oliffi%, p-ethylphenol 61.5% by weight, p-cresol 3.4% by weight, phenol 1.0
% by weight and water 12.12.1% by weight)24,0)
and polystyrene containing a terminal methacryloyl group (manufactured by Toagosei Kagaku Kogyo Co., Ltd., macromonomer As-6; weight average molecular weight 13,600) were placed in a flask, and 7
The mixture was heated and dissolved in a 0C oil bath.

And azobisisobutyronitrile 0.5? Add 7
The mixture was heated at 0CK for 4 hours. The product was poured into hexane, and the resulting precipitate was dissolved in tetrahydrofuran and poured into hexane again. After repeating the operation of dissolving the precipitate in tetrahydrofuran and adding it to hexane two more times, the obtained precipitate was dried under reduced pressure at 80C, and 7. l? Grosspo IJ Y- was obtained. GP of this gloss polymer
The weight average molecular weight of CKj1fE was 22,300, and the number average molecular weight was 6,500. This gloss polymer 2. O
5 methanol and Oy- were added to Y and stirred for 2 hours, and then the solution and precipitate were separated by centrifugation. The solution separated by centrifugation was dried to obtain a 0.60y-solid. This solid has IR spectrum and C-NMR
It was found to be spectrally colored poly-p-vinylphenol, and its weight average molecular weight according to GPCK was 6.80.
It was 0. Further, after drying the precipitate separated by centrifugation, a mixed solvent of toluene-hexane (weight ratio 1:1) 5.0? was added and stirred for 2 hours, and then the solution and precipitate were separated by centrifugation. The thus separated solution was dried to obtain 0.397 solid. This solid is I
It was found from the R spectrum and C-NMR spectrum that it was unreacted polystyrene containing terminal methacryloyl groups (macromonomer As-6). Further, the thus separated precipitate was dried to obtain 0.77p of solid. The weight average molecular weight of this solid by GPC was 32.600, and the number average molecular weight was 9.800.

In addition, the IR spectrum of this solid is shown in Figure 1, 13C-
The NMR spectra are shown in FIG. 2, respectively.

Figure 1 shows that the absorption due to C-H bending of l-substituted aromatic ring is 7
00 and 750cWI, the C-
The absorption due to H bending is 830 cm-', and the phenol C
The absorption due to stretching of -O is 1.230 cm-' K, and the absorption due to stretching of aromatic ring C=C is 1,500 and 1,6
00-, the absorption due to expansion and contraction of phenol OH is 3.3
5000K was seen. The peaks in the C-NMR spectrum shown in FIG. 2 were assigned as follows.

a: 156ppm b:
115ppmd: 137ppm
h: 146ppmc, e% f% g: 1l
26-130pp above IR and 13C-NMR
From the results and the solubility in the solvent, this solid has p
-It was identified as a graft copolymer with a polymer whose main constituent unit is vinylphenol as the main polymer and polystyrene as the branch polymer. Further, from the peak intensity of the C-NMR spectrum, the p-vinylphenol unit/styrene unit molar ratio of this product was calculated to be 29/71.

Example 2 Same crude p-vinylphenol as Example 1 12.0? and a styrene-acrylotrile copolymer containing a terminal methacryloyl group (manufactured by Toagosei Chemical Industry Co., Ltd., Macromonomer AN-6; weight average molecular weight 13.900) 1.7) were placed in a flask and dissolved by heating in an 80C oil bath. 0.31 of azobisisobutyronitrile was added thereto and heated at 80C for 2 hours. A gross polymer of 3.11 was obtained from the product by the same purification method as in Example 1. The weight average molecular weight of this gloss polymer by GPC is 15,600.
The number average molecular weight was 3,800. This gloss polymer 1.0? Toluene s and oLf were added to the mixture and stirred for 4 hours, and then the solution and precipitate were separated by centrifugation. The solution separated by centrifugation was dried to give a 0.1
A solid of 0) was obtained. This solid has an IR spectrum and C-
The NMR spectrum revealed that it was an unreacted styrene-acrylonitrile copolymer (macromonomer AN-6) containing a terminal methacryloyl group. Further, after drying the precipitate separated by centrifugation, methanol 5.
01 was added and stirred for 2 hours, and then the solution and precipitate were separated by centrifugation. The thus separated solution was dried to obtain a 0.28f solid. This solid was found to be poly-p-vinylphenol from the IR spectrum and C-NMR spectrum, and its weight average molecular weight by GPCK was s,ooo. Further, the thus separated precipitate was dried to obtain 0.36% solids. The weight average molecular weight of this solid by GPC was 26,200, and the number average molecular weight was 12.700. Also, the IR of this solid
The vector is shown in Figure 3, and the ESC-NMR spectrum is shown in Figure 4. Figure 3 shows that the absorption due to the C-H bending angle of the monosubstituted aromatic ring is at 690 and 750 an-', and at the 9-position 2
Absorption due to C-1-I bending of substituted aromatic ring is 820cIn
', the absorption due to phenol C-00 stretching is 1.22
0 cm-'', the absorption due to expansion and contraction of aroma*C=C is 1.
510 and 1.600cfP1', absorption due to C=N stretching is 2.230crIT', and phenol Or-
The peak in the 13C-NMR spectrum shown in FIG. 4, in which absorption due to stretching of 1 was observed at 3.380 cm-''K, was assigned as follows.

a: 156ppm b: 115ppmd:
1l37-139pp h:14l41-146p
p, e, f, g: 12l26-130pp: 12
2 ppm Based on the above IR and 13C-NMR results and solubility in the solvent, this solid has a polymer whose main constituent unit is p-vinylphenol as the main polymer, and a styrene-acryloritrile copolymer as the branch polymer. It was identified as a graft copolymer. Furthermore, from the peak intensity of the 13C-NMR spectrum, the molar ratio of p-vinylphenyl units/styrene and acrylonitrile units was calculated to be 23/77.

Example 3 Same crude p-vinylphenol as Example 1 24.0? and polymethyl methacrylate containing terminal methacryloyl group (
Toagosei Chemical Industry @) M, macromonomer AA-6; weight average molecular weight 11,200) 4.4? was placed in a flask and dissolved by heating in an 80C oil bath. 0.51 of azobisin butyronitrile was added thereto and heated at 80CK for 2 hours. 8.2? from the product by the same purification method as in Example 1. A gloss polymer was obtained. The weight average molecular weight of this gloss polymer PCK was 9,800, and the number average molecular weight was 2.800. This gloss polymer 2.0
7 and toluene 5.0? was added and stirred for 2 hours, and then the solution and precipitate were separated by centrifugation. The solution separated by this centrifugation was dried to dryness, but no solid was observed. That is, polymethyl methacrylate containing a terminal methacryloyl group (macromonomer A) as a reaction raw material
Since A-6) is insoluble in hexane and soluble in toluene, it was found that there was substantially no unreacted material. In addition, after drying the precipitate separated by centrifugation, methanol 10% was added and stirred for 2 hours, and then centrifuged at 11fIIc to separate the solution and precipitate. The thus separated solution was dried to obtain 0.90i of solid. This solid was found to be poly-p-vinylphenol from the IR spectrum and C-NMR spectrum, and its weight average molecular weight by GPC was 4,900. Further, the thus separated precipitate was dried to obtain 0.73% solids. The weight average molecular weight of this solid according to GPCK is 1
6,600. The number average molecular weight was 6,600. In addition, the IR spectrum of this solid is shown in Figure 5, 13C-
The NMR spectra are shown in FIG. 6, respectively. Figure 5 shows that the absorption due to C-H bending of the 9-position disubstituted aromatic ring is 820c.
In rn-1, absorption due to stretching of ester C-0-C is 1
, 140 ctn, absorption due to stretching of aromatic ring C=C is 1,510 and 1,600 cW1-1, 1C=O
The absorption due to the stretching of phenol OH was observed at 1,720 c1n', and the absorption due to the stretching of phenol OH was observed at 3,420 ct''K.

The peaks in the 13C-NMR spectrum shown in FIG. 6 were assigned as follows.

a: 156ppm b: 116ppmc
: 129ppm d :12l27-1
29pp:18,20ppm f:4545-
46pp: 52ppm h: 55ppmi
: 178,179 ppm From the above In and 13C-NMR results and solubility in the solvent, this solid has a polymer with p-vinylphenol as the main constituent unit as the main polymer and polymethyl methacrylate as the branch polymer. It was identified as a graft copolymer. Also, from the peak intensity of the 13C-NMR spectrum, p-vinylphenol units/
The molar ratio of methyl methacrylate units was calculated to be 29/71.

Example 4 Same crude p-vinylphenol as in Example 1 24.01 and terminal methacryloyl group-containing polybutyl acrylate (manufactured by Toagosei Kagaku Kogyo Co., Ltd., macromonomer AB-6) 5
．． 57 was placed in a flask and dissolved by heating in a 90C oil bath. And azobisisobutyronitrile 0.6? was added and heated at 90C for 4 hours. A gloss polymer of 6.91 was obtained from the product by the same purification method as in Example 1.

The reaction raw material, polybutyl acrylate containing terminal methacryloyl groups (macromonomer AB-6), is soluble in hexane, and its unreacted substances are removed during the purification process of the product, so the resulting gross polymer does not include the unreacted material. yic by GPCK of this gloss polymer
t average molecule i 9,400. fi average molecular weight is 2,7
It was 00. This gloss polymer 2. O? toluene5. Oz was added and stirred for 2 hours, and then the solution and precipitate were separated by centrifugation. The precipitate separated by this centrifugation was dried to obtain a solid of 0.27). This solid was found to be poly-p-vinylphenol from the IR spectrum and C-NMR spectrum, and the weight average molecular weight determined by 700PC was 5,700. In addition, the solution separated by centrifugation was dried to 1.65%
1 solid was obtained. The weight average molecular weight of this solid by GPC was 10,700, and the molecular weight in thousands was 2,800. Further, the IR spectrum and C-NMR spectrum of this solid are shown in FIG. 37 and FIG. 8, respectively. Figure 7 shows that the absorption due to the C-H bending of the 9-position 2f substituted aromatic ring is 820 crn', the absorption due to the stretching of the ester C-0-C is 1,160 crn', and the absorption due to the stretching of the aromatic ring C=C is 820 crn'. Absorption is 1,510 and 1,610 car'
The absorption due to stretching of K, C=O is 1,730 m', and the absorption due to stretching of phenol OH is 3,400 cIn-1.
It was seen in The peaks of the "'C-NMR spectrum in FIG. 8 were assigned as follows.

a: 156ppm b: 115ppmc
:1l29-130pp d :13l37-13
8pp: 14ppm f: 20p
pmg: 65ppm h: 125ppm
Based on the IR and C-NMR results of Joki and its solubility in solvents, this solid is a graft polymer with a polymer whose main constituent unit is p-vinylphenol as the trunk polymer and polybutyl acrylate as the branch polymer. It was identified as a copolymer. Also, 13C.

From the peak intensity of the NMR spectrum, the molar ratio of p-vinylphenol unit/butyl acrylate unit of this product is 5.
It was calculated as 2/48.

Example 5 p-acetoxystyrene 7.21 and the same terminal methacryloyl group-containing polystyrene 4.6 as used in Example 1
i was placed in a flask and dissolved by heating in a 100C oil bath.

And azobisin butyronitrile 0.3? Add 1
Heated at 00C for 3 hours.

The product was poured into hexane, the resulting precipitate was dissolved in tetrahydrofuran, the product was poured into hexane again to form a precipitate, and the precipitate was dried at 80C to obtain a 9.2-inch gloss polymer. This gloss polymer 4.0? of,
Dioxane 40? , water 10? and hydrochloric acid 10? The mixture was heated at 75C for 5 hours, then poured into water, and the precipitate thus formed was dried under reduced pressure to obtain 3.3 liters of solid. The IR spectrum of this solid had almost no C=0 absorption, indicating that this solid had been deacetylated. 5.01 parts of methanol was added to 2.0 parts of this deacetylated product, stirred for 2 hours, and then the solution and precipitate were separated by centrifugation. The solution separated by this centrifugation was dried to obtain a 0.91y-solid. This solid was found to be poly-p-vinylphenol from the IR spectrum and C-NMR spectrum, and its weight average molecular weight by GPC was 3,000. In addition, after drying the precipitate separated by centrifugation, toluene-hexane (weight ratio 1:1) mixed solvent 5,
O? was added and stirred for 2 hours, and then the solution and precipitate were separated by centrifugation. The thus separated solution was dried to obtain a 0.545' solid. This solid was found to be polystyrene containing unreacted terminal methacryloyl groups from the IR spectrum and C-NMR spectrum.

In addition, the precipitate thus separated was dried to give a concentration of 0.30%.
A solid was obtained.

The weight average molecular weight of this solid according to GPCK is 20.400
The number average molecular weight was 8,700. Further, the IR spectrum and C-NMR spectrum of this solid are shown in FIG. 9 and FIG. 10, respectively. FIG. 9 shows the example IK
The same absorption as in Figure 1 is seen in Figure 10, and in Figure 10,
The same peaks as in FIG. 2 in Example IK were observed. From the above IR and 13C-N MR results and solubility in the solvent, this solid was p-
It was identified as a graft copolymer consisting of a polymer whose main constituent unit is vinylphenol as the trunk polymer and polystyrene as the branch polymer. Also, from the C-NMR spectrum intensity, p-vinylphenol units/
The styrene unit molar ratio was calculated to be 37/63.

[Brief explanation of drawings]

Figures 1 and 2 show the IR spectrum and 13C-NM of the graft copolymer obtained in Example 1, respectively.
Figure 3 and Figure 4 are the IR spectrum and 13C-NMR spectrum of the graft copolymer obtained in Example 2, respectively; Figures 5 and 6 are the Figures 7 and 8 are the IR spectrum and C-NMR spectrum of the graft copolymer obtained in Example 4, respectively; and Figure 9 is the IR spectrum and C-NMR spectrum obtained in Example 3. and FIG. 10 are the IR spectrum and C-NMR spectrum of the graft copolymer obtained in Example 5, respectively.

Claims (2)

[Claims] (1) p-vinylphenol whose hydroxyl group is protected with or without an easily removable protecting group, and a polymer having a methacryloyl group at the end and a monomer other than vinylphenol as a constituent, and/or a polymer whose terminal end is a monomer other than vinylphenol. A method for producing a graft copolymer, which comprises reacting a polymer having an acryloyl group and having a monomer other than vinylphenol as a constituent in the presence of a radical initiator. (2) A polymer that has a methacryloyl group at the end and has a monomer other than vinylphenol as a component, or a polymer that has an acryloyl group at the end and has a monomer other than vinylphenol as a component has a methacryloyl group or acryloyl group at the end. polystyrene, polybutadiene, polyisoprene, polyisobutylene, polyethylene oxide, polytetrahydrofuran, polyvinyl ether, styrene-acryloritrile copolymer,
The method for producing a graft copolymer according to claim 1, wherein the graft copolymer is polymethyl methacrylate, polyethyl acrylate, polybutyl acrylate, or polydimethylsiloxane.