JPH0421687B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel nitrogen-containing copolymer. Its purpose is to provide excellent corrosion resistance, adhesion, and
It is an object of the present invention to provide a resin for coating material having mechanical properties, particularly a resin for electrodeposition coating material. Aminoplast resins are known as nitrogen-containing polymers and are used in paints, adhesives, and the like. However, when these resins are used, there is a problem that corrosion resistance is insufficient. The present inventors have discovered that when a nitrogen-containing copolymer having a special structure is used in a paint, especially an electrodeposition paint, the corrosion resistance of the paint film is improved, and the present invention has been achieved. In particular, the present invention was able to greatly improve the corrosion resistance of the coating film by using a styrene copolymer. A coating method in which paint is deposited on the surface of an object to be coated by electrophoresis using an electrode is generally called electrodeposition coating, and is widely used for car body painting and the like. Electrodeposition coating methods are divided into anionic electrodeposition methods in which the object to be coated serves as an anode, and cationic electrodeposition methods in which the object to be coated serves as a cathode. Among these, the latter cationic electrodeposition method uses the metal of the object to be coated as a cathode, so it is a technique that has the great advantage that there is no elution of metal ions. Currently used compositions for cationic electrodeposition include, for example, reacting an epoxy resin with a secondary amine to convert the epoxy group into α-dialkylamino-
A typical example is one converted to a β-hydroxyethyl group. The present inventors have endeavored to develop a new material for cationic electrodeposition, and as a result, have discovered a novel linear copolymer. That is, the copolymer of the present invention has the structural formula A
A linear styrenic copolymer comprising 3 to 80% by weight of repeating units represented by formula B and 97 to 20% by weight of repeating units represented by structural formula B, and having a number average molecular weight of 1000 to 500000. [In the formula, one of R ₁ and R ₂ is hydrogen, the other is an alkyl group having 2 to 8 carbon atoms, R ₃ is hydrogen or a methyl group, and R ₄ is hydrogen, a hydroxyl group, or a carbon number 1 to 20 alkyl groups. ] In the above formula, one of R ₁ and R ₂ is hydrogen, and the other has 2 to 8 carbon atoms, so it becomes a copolymer with a secondary amino group in the side chain, making use of the reactivity unique to the amino group. It has been found that it is possible to prepare further derivatives by Further, either R ₁ or R ₂ is preferably hydrogen, and the other is an alkyl group having up to 20 carbon atoms, particularly an alkyl group having 2 to 8 carbon atoms. Specifically, ethyl group, n-propyl group,
These include isopropyl group, butyl group, etc. Also R ₁ ,
It is also preferable that R ₂ is an alkyl group. Specifically, R ₁ and R ₂ are selected from methyl group, ethyl group, or the like. The substituted aminoethyl group, which is a side chain substituent in structural formula A, may be bonded to any position relative to the main side. R ₃ in structural formula B is hydrogen or a methyl group, with hydrogen being particularly preferred. R ₄ is preferably hydrogen, a hydroxyl group or an alkyl group having 1 to 20 carbon atoms. _R1 ． _R2 ,
R ₃ and R ₄ are not limited to one type each, and mixtures of two or more types are also included in the present invention. There is no limit to the weight fraction of the moiety represented by structural formula A based on the total copolymer, but it is preferably 1 to 90% by weight, more preferably 3 to 80% by weight. There is no limit to the weight fraction of the moiety represented by structural formula B in the copolymer, but it is preferably 99 to 10% by weight, more preferably 97 to 20% by weight. As the fraction of the portion represented by structural formula A increases, the specific conductivity in electrodeposition tends to increase. Although there is no restriction on the molecular weight of the copolymer AB of the present invention, it is preferable that the number average molecular weight is 1,000 to 500,000. Furthermore, in the copolymer AB of the present invention, part of the portion represented by the structural formula B in its structure can be replaced with a repeating unit structure represented by the following formula H. In the formula, X is a group selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, and a halogen, Y is a nitrile group,
Hydroxyl group, alkoxy group, acetoxy group,
Aryl group, arylalkyl group, cycloalkyl group, alkenyl group, hydroxyalkyl group, hydroxycycloalkyl group, hydroxyaryl group, hydroxyarylalkyl group, haloalkyl group, haloaryl group, haloarylalkyl group, haloalkylaryl group, aminoalkyl group , aminocycloalkyl group, aminoaryl group, aminoarylalkyl group, aminoalkylaryl group, aminohydroxyalkyl group, aminohydroxyaryl group, pyridyl group, furyl group, tetrahydrofuryl group, pyrrolyl group, imidazolidinyl group, pyrazuridinyl group, piperidyl group group, piperazinyl group, morpholinyl group, pyrrolidonyl group, piperidonyl group, alkylpyridyl group,
or a group selected from arylpyridyl groups, or (However, R ₂₀ to _{R 22} are hydrogen, alkyl groups with up to 20 carbon atoms, hydroxyalkyl groups, glycidyl groups, aminoalkyl groups, aminocycloalkyl groups, aminoaryl groups, aminoarylalkyl groups, aminoalkylaryl groups, aminohydroxy It represents a group selected from an alkyl group, a dialkylaminoalkyl group, a dialkylaminohydroxyalkyl group, and a dihydroxyalkylaminoalkyl group, and n represents an integer of 1 to 50. It represents a group selected from halogen. Copolymer AB can be obtained by copolymerizing monomers having structures represented by the following formulas C and D. The definitions and preferred examples of R ₁ , R ₂ , R ₃ and R ₄ are as described above. That's right. A general method for producing monomer C is to prepare an amine represented by the following structural formula E (hereinafter referred to as "amine E" or simply "amine") in the coexistence of the corresponding alkali metal amide F, It is reacted with divinylbenzene. (In the formula, R ₁ and R ₂ have the same meanings as above, and M
represents an alkali metal. ) As divinylbenzene, p-divinylbenzene, m-divinylbenzene, or a mixture thereof can be used. Furthermore, although commercially available divinylbenzene contains ethylvinibenzene as an impurity, such crude divinylbenzene can also be used. However, when crude divinylbenzene is used as a starting material, a product derived from ethylvinylbenzene may be produced as a by-product. p-Divinylbenzene is more preferable as a raw material because of its high reaction rate and the fact that by-product G, which will be described later, is less likely to be produced. As the amine, a primary amine or a secondary amine can be used, but methylamine and ammonia have low reactivity and are not preferred. Examples of primary amines include ethylamine, n-propylamine, isopropylamine, n-butylamine,
Alkylamines such as sec-butylamine, tert-butylamine, pentylamine, 2-ethylhexylamine, dodecylamine, octadecylamine, cycloalkylamines such as cyclohexylamine, cyclopentylamine, unsaturated amines such as allylamine, benzylamine, alinine, etc. , is a primary amine having a hydrocarbon group. Examples of secondary amines include dialkylamines such as dimethylamine, diethylamine, diprobylamine, diptylamine, and dioctylamine, dicycloalkylamines such as dicyclohexylamine and dicyclopropylamine, cyclic amines such as ethyleneimine, and unsaturated amines such as diallylamine. Amine is a secondary amine having a hydrocarbon group. Furthermore, diamines or triamines such as ethylenediamine, trimethylenediamine, hexamethylenediamine, octamethylenediamine, dodecamethylenediamine, diethylenetriamine, dipropylenetriamine, N-methylethylenediamine, N-ethylethylenediamine, and N,N'-diethylethylenediamine are also used. be able to. When a primary amino group and a secondary amino group coexist in one molecule, generally the more reactive secondary amino group is selectively added to the side chain double bond of polydivinylbenzene. Among these, ethylamine, n-propylamine, isopropylamine, butylamine, N-methylethylenediamine, and N-ethylethylenediamine are particularly preferred. Since amine causes a stoichiometric reaction with divinylbenzene, compound [C] can be easily synthesized by adjusting the amount of amine used. Preferred representative examples of the monomer C produced in this way include ethylaminoethylstyrene, isoprolaminoethylstyrene, dimethylaminoethylstyrene, diethylaminoethylstyrene, di(aminoethyl)aminoethylstyrene, N, Examples include N-aminoethylmethylethylstyrene ( _R1 = _CH3 , _R2 = _CH2 - _CH2 - _NH2 ).
Typical examples of monomers represented by structural formula D, that is, styrene derivatives, include styrene, halostyrenes such as α-methylstyrene, chlorostyrene, and bromustyrene; alkylstyrenes such as hydroxystyrene, ethylstyrene, and propylstyrene; styrene,
Examples include ethoxystyrene and ptoxystyrene.
Other copolymerization components include acrylic esters, methacrylic esters, vinyl chloride, acrylonitrile, vinylidene chloride, methyl vinyl ketone, vinyl compounds such as vinyl acetate, butadiene,
It is also possible to add dienes such as isobrene, and vinyl group-containing compounds such as vinylpyridine and vinylpyrrolidone. The polymerization method may be ionic polymerization or radical polymerization, but copolymerization is preferably carried out in the presence of a radical initiator. As for the polymerization operation, any of the general polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used. As a radical initiator, benzoyl peroxide,
Peroxides such as dilauroyl peroxide, azo compounds such as azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpaleronitrile), 1,1'-azobiscyclohexane-1-carbonitrile Representative examples include hydroperoxides such as , cumene hydroperoxide and t-butyl hydroperoxide, and persulfates such as potassium persulfate and ammonium persulfate. Adjustment of the molecular weight of the copolymer can be achieved by adjusting the amount of initiator used or by carrying out solution polymerization in a system in which a solvent or a chain transfer agent is added. Increasing the amount of initiator will decrease the molecular weight. The amount of these initiators used is preferably 0.05 to 10% by weight, more preferably 0.2% based on the monomer.
and 5% by weight. As a solvent or chain transfer agent, toluene,
Examples include aromatic hydrocarbons such as ethylbenzene, cumene, and diphenylmethane, halogenated hydrocarbons such as carbon tetrachloride and chloroform, aliphatic alcohols such as n-butanol and isopropanol, and mercaptans such as n-butylmercaptan. The amount of the solvent or chain transfer agent used is not particularly limited, but it is preferably 0.1 to 40 times the weight of the monomer.
Further, an equivalent amount to 20 times the amount is preferable. The polymerization temperature is preferably 0°C to 150°C, more preferably 40°C to 100°C. Various methods known in the art can be used to isolate the copolymer AB obtained by the above method, but in the case of solution polymerization, it can be isolated in a solvent that does not dissolve the copolymer produced. Preferred are a reprecipitation method in which the reaction mixture is charged, and a steam distillation method in which the reaction mixture is heated while blowing steam to distill off the solvent and unreacted monomers. In the case of suspension polymerization, it is recommended to separate the obtained granular product and wash it thoroughly with water or the like to remove the suspension aid, suspension aid, etc. adhering to the surface of the product. As means for confirming the structure of the obtained copolymer, general methods such as elemental analysis, infrared absorption spectroscopy, and magnetic resonance spectroscopy are used.
Furthermore, the composition of the copolymer can be estimated by quantifying unreacted monomers by gas chromatography or liquid chromatography after polymerization.
Molecular weight is measured by viscosity method and gel vermi-ation chromatography. Light scattering method, osmotic pressure method, vapor pressure osmometry, etc. are used. The copolymer AB of the present invention exhibits excellent properties when used in various applications, such as paints, adhesives, inks, surface treatment agents, and molding materials. It is particularly useful as a coating component for paints. In other words, it has become clear that the coating film made of copolymer AB exhibits good durability. A coating film can also be obtained by dissolving copolymer AB in a solvent and applying it, and then evaporating the solvent, or by applying an aqueous dispersion of copolymer AB and then evaporating the water. is reacted with copolymer AB with acid HX,
Part or all of the structure represented by formula A can be replaced by formula A' (In the formula, X represents an acid group.) After replacing the structure with membrane can be obtained. That is, coating film formation is achieved by using the object to be coated as a cathode and passing a direct current between it and the anode. Such a cationic electrodeposition method is the most preferred method for forming a coating film made of the present copolymer. There are no particular restrictions on the acid HX, but examples include hydrochloric acid, sulfuric acid, nitric acid, chromic acid, perchloric acid, phosphoric acid, mineral acids such as carbonic acid, acetic acid, propionic acid, butyric acid,
Aliphatic carboxylic acids such as caproic acid, hydroxycarboxylic acids such as glycolic acid and lactic acid, malonic acid,
Dicarboxylic acids such as adipic acid, aromatic carboxylic acids such as benzoic acid, phthalic acid, and salicylic acid, alkanesulfonic acids such as methanesulfonic acid and ethanesulfonic acid, and arylsulfonic acids such as benzenesulfonic acid, toluenesulfonic acid, and laurylbenzenesulfonic acid. Among these, organic carboxylic acids are preferred, and acetic acid, lactic acid, hisaroxyacetic acid, and the like are more preferred because they can keep the electrolyte near neutrality. The amount of acid added is preferably 0.1 to 5 times the amount of nitrogen in copolymer AB, more preferably 0.3 to 2 times the amount of nitrogen in copolymer AB. In the neutralization reaction, only the copolymer and the acid may be mixed, but when the acid is solid or when reacting with less than an equivalent amount of the acid, it is recommended to use a solvent. As the solvent, a water-soluble organic solution such as alcohol or ketone is preferable. Among these, lower alcohols such as methanol, ethanol, and propanol, acetone, and methyl ethyl ketone are particularly preferred. The amount of solvent is 10% to 300% by weight based on copolymer AB.
is preferred, and 20% to 150% is more preferred.
The temperature of the neutralization reaction is preferably -20°C to 200°C,
More preferably, the temperature is 10°C to 150°C. The amount of water used to prepare the electrolyte is
It is preferably at least 30 times the weight of copolymer A'B, more preferably at least 5 times and at most 20 times the weight.
The pH of the electrolytic solution prepared here is preferably 3-8, more preferably PH5-7. Copolymer A′B has the following structural formula () It can also be produced by copolymerizing a monomer mixture containing the monomer represented by and monomer D. This monomer is a monomer represented by formula C, which is converted into an acid HX
It can be easily produced by neutralizing with In the case of copolymerization of monomers I and D, radical polymerization is preferred, and solution polymerization in a highly polar solvent is recommended. When water is used as a solvent, in addition to water-soluble initiators mentioned above, redox initiators consisting of combinations of persulfate/bisulfite, chlorate/sulfite, etc. can also be used. . Typical examples of this redox initiator are combinations such as potassium persulfate/sodium bisulfite, sodium chlorate/sodium sulfite, and the like. Typical examples of the material for the cathode, that is, the surface to be coated, include zinc phosphate-treated ore plates, iron phosphate-treated ore plates, untreated ore plates, galvanized ore plates, cascading ore plates, aluminum, copper, and copper alloys. be. As an anode,
Stainless steel plates, carbon plates, etc. are preferred. There is no limit to the voltage between the poles, but 50V to 500V is preferable.
Particularly preferred is 100V to 400V. Electrodeposition time is 10
The time period is preferably from seconds to 20 minutes, and more preferably from 1 minute to 10 minutes. The temperature of the electrodeposition solution is preferably 0°C to 60°C, more preferably 10°C to 40°C. Examples will be described below, but the present invention is not limited thereto. Note that reference examples are also shown. Reference Example 1 (Monomer production method) 1-1 A stirrer, a thermometer, and a reflux device are prepared in a three-necked flask 2 purged with nitrogen, and 44 ml of purified tetrahydrofuran is added using a dropping funnel. Add 86 ml of isopropylamine while stirring, and add n
- When 20 ml of a 2N solution of butyl lithium was added, the color of the solution changed from clear and colorless to pale yellow.
This flask was placed in a constant temperature bath at 30°C, and 148 ml of P-dipinylbenzene was added while stirring. The reaction mixture was orange in color, and after reacting for 3 hours, 1 ml of methanol was added, and 2 ml of methanol was added.
water. Extraction was performed twice with n-hexane, the oil layer was dried over magnesium sulfate overnight, and then distilled. 0.07mmHg as product
11.8g of a fraction having a boiling point around 67°C was obtained. It was confirmed from the following spectral data that this product was P-(isopropylaminoethyl)styrene. Proton nuclear magnetic resonance spectrum (100MHZ, solvent: deuterated chloroform, reference material TMS), δ value;
0.8 (1H), 0.96 (double line, J = 7HZ, 6H), 2.6~
2.9 (multiplet, 5H), 5.1 (doublet, J=11HZ,
1H), 5.6 (doublet, J=18HZ, 1H), 6.6 (two sets of doublets, 1H), 7.0-7.35 (multiplet, 4H). Infrared absorption spectrum (liquid film); 3300, 1630,
1510, 1470, 1380, 1080, 990, 910, 835 cm ^-1 . 1-2 After putting 80 ml of n-hexane that has been dried and distilled over sodium metal into a stainless steel pressure-resistant reaction device with an internal volume of 200 ml and equipped with a stirring device, the device is sufficiently cooled from the outside with a dry ice-methanol mixture. did. An ethylamine cylinder (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was connected to the apparatus, and the valve was opened to introduce ethylamine into the reaction apparatus. From the change in the weight of the cylinder before and after introduction, it was confirmed that 6.3g of ethylamine had been introduced. 8.4 ml of n while stirring
- A 15% n-hexane solution of butyl lithium was introduced. Next, add 18.2 g of P to 40 ml of dry n-hexane.
- A solution containing divinylbenzene was introduced. The reactor was placed in a 25°C water bath and stirred for 5 hours, then 0.5g of methanol was added to the reaction mixture and the mixture was heated to 200°C.
ml of water. Extraction was performed twice with n-hexane, the oil layer was dried over magnesium sulfate overnight, and then distilled. 72℃ to 73℃ at 0.31mmHg
14.7 g of a distillate having a boiling point of 14.7 g was obtained. It was confirmed by gas chromatography that it was a single substance.
The refractive index of this fraction was 1.538 (NaD line) at 22°C. The spectroscopic analysis results were as follows. Infrared absorption spectrum; 3280, 1620, 1510,
1120, 985, 900, 820 cm ^-1 . Nuclear magnetic resonance spectrum [100MHZ, tetramethylsilane (TMS) standard], δ value: 0.80 (single line,
1H), 1.04 (triple line, J=7.2HZ, 3H), 2.55 (4
Multiplet, J=7.2HZ, 2H), 2.6~2.8 (multiplet,
4H), 5.08 (double line, J=10.5HZ, 1H), 5.60 (2
Double line, J=17.8HZ, 1H), 6.56 (two sets of double lines,
J=10.5, 17.8HZ, 1H), 6.9~7.3 (multiplet,
4H). Here, J is the coupling constant, nH is hydrogen n
This indicates that the amount is equivalent to 1. These analytical results indicate that the product is var(β-ethylaminoethyl)styrene. 1-3 In a four-necked flask equipped with a corrugated condenser, a thermometer, and two dropping funnels, and containing a magnetic rotor, n- was distilled after drying with sodium metal.
100 g of hexane was added, and the mixture was sufficiently cooled from the outside with a methanol and dry ice mixture. After circulating dry ice-methanol in the cooler, a dimethylamine cylinder (manufactured by Tokyo Chemical Industry Co., Ltd.) was connected to the tip of the cooler, and the valve was opened to introduce dimethylamine into the flask. It was confirmed from the change in the weight of the cylinder before and after introduction that 115.4g of dimethylamine had been introduced. While stirring the n-hexane solution of dimethylamine with a magnetic rotor, 77 g of a 15% hexane solution of n-butyl lithium was added dropwise from the dropping funnel at such a rate that the temperature of the mixture did not exceed -60°C. As n-butyllithium was added dropwise, the liquid turned pale yellow. Next, a mixed solution of 435 g of dry hexane and 332 g of baladivinylbenzene prepared by the method described below was added dropwise from the second dropping funnel at a rate such that the internal temperature did not exceed -60°C. The reaction solution turned pale green. After the dropping was completed, stirring was continued for 3 and a half hours, and the internal temperature rose to -20°C. When a portion of the sample was sampled and divinylbenzene was quantitatively determined using a gas chromatograph, it was determined that the starting concentration was 15%, so 10 ml of methanol was added to terminate the reaction. The reaction mixture was added to the water in Step 1, extracted twice with n-hexane, and then the oil phase was dried over magnesium sulfate overnight, and after the magnesium sulfate was separated, vacuum distillation was performed. 75℃ to 80℃ at 0.4mmHg
250 g of a fraction with a boiling point of . Analysis by gas chromatography showed that the purity was over 98%, and although some raw material divinylbenzene was included, the main component was a single peak (filling material: silicon DC-550, column length; 1m, column temperature: 150℃, carrier gas: nitrogen, flow rate: 136
ml/min, retention time: 3.2 minutes). The specific gravity of this fraction is
The refractive index was measured to be 0.913 at 23°C and 1.534 (NaD line) at 23°C. Analyzes were conducted to confirm the structure using high-purity samples obtained by fractionation using gas chromatography. The results are shown below. Elemental analysis; C: 82.08%, H: 9.86%, N:
8.07% Infrared absorption spectrum; 2920, 2740, 1620,
1500, 1440, 1250, 1130, 1030, 980, 890, 820
cm ^-1 proton nuclear magnetic resonance spectrum; (measurement solvent:
Carbon tetrachloride) δ value (reference material: TMS deuterium chloroform solution) 2.07 (singlet, 6H); 2.2 to 2.7 (4H)
5.00 (double line, J = 11 Hz, 1H); 5.50 (double line,
J = 18 Hz, 1H); 6.55 (two sets of double lines, J =
11 Hz and 18 Hz, 1H); 6.8 to 7.3 (4H) Note that J here indicates the coupling constant,
Also, 1H represents the equivalent of one hydrogen. These analytical results indicate that the product is para-dimethylaminoethylstyrene. 1-4 Put 26g of P-divinylbenzene and 40ml of cyclohexane into a 200ml three-necked flask. moreover
Amide prepared from 14.8g diethylamine and 0.512g butyllithium. Add 40 ml of cyclohexane solution of amine mixture and heat at 50°C with stirring for 30 minutes.
heated for an hour. Then add 10ml of methanol,
The reaction solution was distilled to obtain 29 g of P-diethylaminoethylstyrene having a boiling point around 84° C. at 1 mmHg. This product gave an infrared absorption spectrum with the following characteristic absorption. 1800, 1620,
1505, 1195, 1060, 980, 895, 820 cm ^-1 , and elemental analysis showed C: 82.65%, H: 10.58
%, N: 6.80%. The results of these analyzes are
The product is shown to be para-diethylaminoethylstyrene. Example 1 In a 2-volume separable flask equipped with a stirring bar, thermometer, and reflux condenser, 913 g of toluene, 130 g of styrene, 16.0 g of P-isopropylaminoethylstyrene synthesized in Reference Example 1-1, and 2.2'-azo Add 2.7g of bisisobutyronitrile to 80%
Stirring was continued for 36 hours. After the reaction, the amount of residual monomer was determined by gas chromatography, and it was found that P-
12.8% of isopropylaminoethylstyrene and 5.1% of styrene were unreacted. Steam was introduced into the reaction mixture from a steam generator, and unreacted monomers and toluene were steam-distilled. After cooling the obtained copolymer, it was crushed and dried. Yield 123g,
Elemental analysis of the produced copolymer showed C; 91.17%, H;
8.13%, N: 0.70%. In addition, the following characteristic absorption was observed in the infrared absorption spectrum.
3050, 2930, 1600, 1490, 1410, 760, proton nuclear magnetic resonance spectra gave the following results. Solvent; deuterated chloroform, reference material;
TMS, δ value (ppm); 0.8~1.2, 1.2~2.6, 2.7~
3.1, 6.2-7.4. Further, when the intrinsic viscosity of the dioxysan solution was measured, it was 0.011 at 25°C. Example 2 In a 2-volume separable flask, 1170 g of tamene, P-isopropylaminoethylstyrene 12.4
Add 154 g of P-hydroxymethylstyrene, and 8.1 g of 2.2'-azobisisobutyronitrile, and after blowing nitrogen at room temperature for 5 minutes, seal the container tightly.
After continued heating at .degree. C. for 36 hours, steam distillation was carried out in the same manner as in Example 1. Elemental analysis of the obtained copolymer was C; 80.7%,
H: 7.8%, O: 10.9%, N: 0.6%. The infrared absorption spectrum showed the following absorption. 3320,
3040, 2930, 1600cm ^-1 . Further, the intrinsic viscosity measured with a dioxane solution was 0.007. Example 3 In a 2-volume separable flask equipped with a stirring bar, thermometer, and reflux condenser, 1100 g of toluene, 154 g of P-vinyltoluene, 17.0 g of P-isopropylaminoethylstyrene, and 2,2'-azobisiso were added. After adding 8.3 g of butyronitrile and continuing stirring at 75° C. for 36 hours, steam distillation was performed in the same manner as in Example 1. The elemental analysis value of the obtained copolymer was C; 90.1%,
H: 9.2%, N: 0.70%. Further, the intrinsic viscosity measured with a dioxane solution was 0.008. Example 4 and Reference Examples 2 and 3 The solvents and monomers shown in Table 1 were added to a 5-separable flask equipped with a stirring bar, a thermometer, and a reflux condenser, heated, and reacted at 70°C for 36 hours. I did it. After the reaction, the residual monomer was quantified by gas chromatography. Gas chromatographic analysis values are shown in Table 2. After the reaction, the reaction product was reprecipitated by adding 3 times the amount of hexane, and the polymer was isolated and dried under reduced pressure. The results of elemental analysis are shown in Table 3.

【table】

【table】

[Table] In the infrared absorption spectrum of Example 4, the following characteristic absorptions were obtained. 3050, 2930, 1720, 1600,
760,700cm ^-1 . The nuclear magnetic resonance spectrum of Example 4 had the following results. Solvent: Deuterated chloroform, Reference material: TMS, Value (ppm): 0.9.0.96, 1.1~2.4, 2.6~2.9, 3.6, 6.3~
6.8, 6.8~7.3. Moreover, when the intrinsic viscosity of the dioxane solution was measured, it was 0.014, 0.017, and 0.016 in each of Examples 4 to 6 at 25°C, respectively. Example 5 Partially saponified polyvinyl alcohol (degree of saponification 88%, viscosity of 2% aqueous solution 23CP
) 4g, sodium chloride 8g and 800ml of pure water
Styrene 140.3 at 60 °C with stirring and dissolved in
g, Pn-propylaminoethylstyrene 16.7
g, 1.6 g of 2,2'-azobis(2,4-dimethylvaleronitrile) is added. Heating was continued at 80° C. for 18 hours while stirring. After the reaction, the product was thoroughly washed with warm water and dried. Diameter 40~
The elemental analysis value of the 500μ granular copolymer is C; 91.3
%, H: 7.9%, N: 0.8%. Example 6 30g of methyl methacrylate in a 500ml beaker,
P-isopropylaminoethylstyrene 56.7g,
50 g of styrene, 1 g of V-50 (2,2'-azobis2aminodipropanone hydrochloride (manufactured by Wako Pure Chemical Industries)),
Add 10 g of Emulgen-950 (polyoxyethylene nonylphenyl type surfactant (manufactured by Kao Atlas)) and 120 g of water, stir at high speed with a homomixer,
A monomer emulsion was prepared. stirrer, stirring rod,
After adding 100 g of water to a separable flask equipped with a reflux condenser and a thermometer and raising the temperature to 80°C, the above emulsion was added dropwise at a rate of 60 g/hr, during which time the reaction temperature was maintained at 80°C. After the dropwise addition was completed, the mixture was reacted at 80°C for 4 hours to obtain a white homogeneous emulsion. In this emulsion
After adding 500 g of methanol to precipitate the polymer, it was dried. The weight of dry polymer is
It weighed 136.5g. Dioxane 30 to this polymer
After adding 500 g of methanol and dissolving the mixture, 500 g of methanol was added and the mixture was reprecipitated, followed by filtering and drying. The yield of the obtained polymer was 136.1 g, and the elemental analysis value was C; 80.3%.
H: 8.8%, O: 7.6%, N: 3.3%. Furthermore, when we measured the intrinsic viscosity of a dioxane solution, we found that
It was 0.009 at 25℃. Example 7 and Reference Examples 4 and 5 The solvents and monomers shown in Table 4 were added to a separable flask equipped with a stirring bar, a thermometer, and a reflux condenser, heated, and the reaction was carried out at 70°C for 36 hours. Summer. introducing steam from a steam generator into the reaction mixture;
Unreacted monomers and toluene were steam distilled.
After cooling the obtained copolymer, it was crushed and dried. The results of elemental analysis of the product are shown in Table 5.

【table】

[Table] Example 8 and Reference Examples 6 and 7 The solvents and monomers shown in Table 6 were added to a one-separate flask equipped with a stirring bar, thermometer, and reflux condenser, heated, and heated at 60°C for 40 A time reaction was performed. Steam was introduced into the reaction mixture from a steam generator, and unreacted monomers and benzene were steam-distilled. After cooling the obtained copolymer, it was crushed and dried. The results of elemental analysis of the product are shown in Table 7.

【table】

【table】

[Table] Example 9 Add 400 ml of ethylbenzene to a 1-volume pressure-resistant glass bottle.
g, P-isoprokepylaminoethylstyrene 20
g, 130 g of styrene, and 3.5 g of 2,2'-azobisisobutyronitrile were added, and a rubber stopper was added, followed by a crown-shaped pressure-resistant stopper with a hole in the top. Next, 1.3 of 10.2g
- Butadiene was introduced from the cylinder through a syringe needle into a pressure bottle. The contents were magnetically stirred at 75°C for 32 hours. After cooling, the reaction mixture was subjected to steam distillation, and the resulting copolymer was dried after cooling. Elemental analysis of the dried copolymer was as follows. C; 90.9%, H; 8.2
%, N; 0.9%. The results of the proton nuclear magnetic resonance spectrum were as follows. Solvent: Deuterated chloroform, Reference material: TMS, δ value (ppm): 0.8-1.2,
1.2~2.6 4.7~5.2, 5.2~6.0, 6.2~6.8, 6.8~7.4.
Furthermore, the intrinsic viscosity of the dioxane solution was measured and found to be 0.012 at 25°C. Example 10 A homogeneous solution of 20 g of the copolymer obtained in Example 1 in xylene was applied onto an untreated steel plate of 0.3 x 50 x 150 mm using a bar coater so that the dry coating film was 10 μm. After drying the resulting coating film at 100° C. for one day, a goblin adhesion test was performed and the result was 100/100.
In addition, the bending test was passed at 1 mm. Example 11 23.6 g of the copolymer obtained in Example 1 was added to 23.6 g of ethylene glycol monobutyl ether,
The mixture was heated to 70°C and mixed uniformly. 0.4 g of acetic acid was added to this and stirred until homogeneous. When 80 ml of deionized water was added to 32 g of this mixed liquid while stirring at room temperature, the pH of the liquid became 7.8. When a direct current was passed through this solution using a 0.8 x 70 x 150 mm untreated steel plate as a cathode and a stainless steel anode as a counter electrode, electrodeposition was achieved at 200 V for 60 seconds. Separately measuring the specific conductivity of the same liquid
It was 1600μmho/cm. The Erichsen value of the resulting coating film was 10 mm, cross-cut adhesion (1 mm width cross cut) 100/100, Dupont impact resistance 1 Kg x 50 cm, 1/2
It passed the inch mark. Example 12, 13 Using the mixed solution listed in Table 8, Example 11
conducted a similar experiment. The results are shown in Table 9. The coating film was uniform and smooth with few pinholes.

【table】

【table】

Claims (1)

[Claims] 1 3 to 80% by weight of repeating units represented by structural formula A and 97 to 80% by weight of repeating units represented by structural formula B
20% by weight, with a number average molecular weight of 1000 or more.
500,000 linear styrenic copolymer. [In the formula, one of R ₁ and R ₂ is hydrogen, the other is an alkyl group having 2 to 8 carbon atoms, R ₃ is hydrogen or a methyl group, and R ₄ is hydrogen, a hydroxyl group, or a carbon number 1 to 20 alkyl groups. 2. The copolymer according to claim 1, wherein the alkyl group is an ethyl group, an n-propyl group, or an isopropyl group.