DE2216175C3 - Process for emulsion polymerization of vinyl monomers - Google Patents

Description

The invention relates to a process for the polymerization of vinyl monomers in aqueous Media using an emulsifier. The aqueous emulsions of Vinyl polymers are useful as solvents for paints and adhesives.

In general, emulsion polymerization of vinyl monomers is mainly using of a low molecular weight emulsifier. If the through the above procedure obtained polymer emulsion is used as a coating composition, however, the coating film obtained therefrom has poor water resistance. It is suggested on the other hand been carried out, the emulsion polymerization of vinyl monomers in the presence of a high molecular weight Execute emulsifier that has a hydrophilic side chain attached to an oleophilic main chain is bound. such as polyacrylic acid, polymethacrylic acid and polyvinyl pyridine. However, it lies no report yet on the use of the resulting emulsion as a coating composition settlement and about the properties of the obtained from it Coating film.

The object of the invention is therefore a process for the emulsion polymerization of vinyl monomers using a high molecular weight emulsifying agent, the resulting Polymer emulsion as a carrier door paints, adhesives and compositions for resin treatment is useful.

The invention relates to a process for the polymerization of vinyl monomers in aqueous media using an emulsifying _{agent which is characterized in that a vinyl monomer J ^^ ,, maleic acid} and its one of the vermnuui.gc addition «

Anhydride can be used where ^d ^ ^Add "'°""product one Saxu-ezah ™ 20 ^^ S and to the ^^
added we-d, there

on the ^{total solids contained in the e} f ff V ^^ S 5 hk, in the range of 5 b, s 150.

That ^!

medium includes a ^. ^^^

tion product euies But ^ en npolyme with emenv average Mokkula JJ T ^ ^of ^ 's 40000, and at least one of the compounds maleic acid and maleic anhydride, the Addn.onsprodukt has an acidity from 20 to 350.

On the basis of the invention, fat ^ «dh. that the above specific ^Em ^ "^ ™ ^ttU ^. maleized butadiene polymer is effective for roughening polymerisation of certain, Artu, nV n> I-

Use of the above emulsifying agent Invention obtained aqueous emulsion of Vm \ lpolymeren Can be effectively used as a vehicle for paints to make a glossy coating film manufacture that has a high degree of hardness. Water resistance and mechanical Has strength with a smooth, cohesive surface that is free of undesirable stickiness The reason why such excellent coating films by the method of the present invention can be prepared using the above emulsifying agent is attributable to the fact that used as emulsifying agents and in the resulting aqueous emulsion of vinyl polymers contained molecules of the maleinized Butadiene polymers to form a three-dimensional Network structure react with each other during the film formation process. Furthermore, the Polymer emulsion so excellent dye dispersibility on that the pigment used never comes out of it during the film formation process is deposited, making it possible to form a coating film to achieve with excellent shine. The polymer emulsion obtained according to the invention is also suitable as an adhesive and compound for synthetic resin treatment.

Dhs used as a raw material for producing the emulsifier used in the present invention Butadiene polymer contains homopolymers of butadiene, mixed polymers of butadiene with other copolymerizable monomers and modified products of these homopolymers u »id Mixed polymers. The homopolymer of butadiene polymers can have a structure of 1,2-vinyl bond, Iran-1,4-bond, cis-1,4-bond and their mixtures. In particular, polybutadiene, which contains more than 80% 1,2-vinyl bonds is preferred. When emulsion polymerization is carried out using an emulsifying agent, that by maleinizing a polybutadiene that contains such a large amount of 1,2-vinyl bond, was obtained, occurs in an effective manner graft polymerization of the vinyl monomer with the maleini-

Sized butadiene polymers during the polymerization process, whereby the from the polymer emulsion obtained coating film can be sufficiently cured without using a curing agent can be used to produce a cured film exhibiting a higher degree of water resistance.

The copolymers of butadiene are those which contain at least 10 percent by weight, preferably at least 40 percent by weight, of butadiene. The monomers to be copolymerized with butadiene contain z. B. olefins having 2 to 6 carbon atoms; Dienes such as isoprene, chloroprene and cyclopentadiene; Acrylic acid, methacrylic acid and their alkyl (C _{1 - to C lb} -) esters, etyrene compounds, such as styrene, -methylstyrene and vinyl toluene and acrylonitrile and methacrylonitrile.

The modified products of the HomopoJymeren and the interpolymer of butadiene include e.g. B. partially hydrogenated butadiene polymers, cyclized Butadiene polymers, hydroxyl butadiene polymers and epoxidized butadiene polymers. It is preferred that the modified butadiene polymer is greater than 60% of that in the original butadiene polymer retained double bonds.

The butadiene polymers used for the process of the invention have an average Molecular weight from 2 (X) to 40,000. When the average molecular weight is less than 2 (X) is, the emulsifying agent obtained therefrom does not produce a vinyl polymer emulsion having good storage stability and which is capable of providing a coating film having excellent properties. If the butadiene polymer has an average molecular weight of more than 40,000, it is Viscosity too high to cause the subsequent maleinization reaction. A preferred average The molecular weight of the butadiene polymer is in the range of 500 to 10,000.

To produce the emulsifier used according to the invention, the butadiene polymer is used with Maleic acid and / or its anhydride maleinisierl, and there is an addition product of the two Links. The amount of maleic acid or its anhydride used varies over one wide range depending on the type of butadiene polymer, but it is necessary. Maleic acid or its anhydride to use in an amount sufficient to contain a maleinized butadiene polymer having an acid number in the range from 20 to 350. Usually this amount is in the range of 1.7 to 200 parts by weight, preferably 3.5 to KX) parts by weight, based on 100 parts by weight of the butadiene polymer. The MaWnisierungsreaktion can be carried out with stirring in a protective gas atmosphere, wherein, if desired, an organic solvent is used will. Examples of the solvents are aromatic hydrocarbons such as benzene, Toluene and xylene; and ketones, such as acetone, methyl ethyl ketone and methyl isobulyl ketone: Esters such as ethyl acetate, methyl acetate. Butyl acetate; Ethers such as dioxane, tetrahydrofuran and dipropyl ether. The preferred reaction temperature is in the range from 150 to 250 C. The reaction is usually complete within 0.5 to 40 hours.

The addition product of butadiene polymer and maleic anhydride then undergoes a conventional ring opening reaction subjected using water, alcohols or amines. The use of water leads to dicarboxylic acid compounds, of Alcohols to half-esters and amines to half-esters

S amides. The alcohols used are, for example, -dliphatic monohydric alcohols with 1 to 18 carbon atoms, Ethylene glycol, propylene glycol, polyethylene glycol with a molecular weight of not more than 1500 and polypropylene glycol with one

ίο molecular weight not exceeding 2000, and the Amines used include, for example, methylamine, ethylamine, dimethylamine and diethylamine.

The acid number of the addition product obtained should be in the range from 20 to 350 Hegen. The addition product with an acid number of less than 20 does not show a sufficient effect as an emulsifying agent, while those with an acid number greater than 350 result in the formation of a coating film which has poor water resistance. The preferred acid number is in the range from 20 to 200.

The addition product is then neutralized with a base to be used in the process of the invention to produce emulsifiers used. The base used includes, for example, ammonia, alkali hydroxides, Alkali oxides, alkali carbonates, alkali bicarbonates and amines such as methylamine. Ethylamine, propylamine, butylamine, stearylamine and methanolamine, primary amines. Dimethylamine, diethylamine, Methylethylamine and diethanolamine, secondary amines and trimethylamine, triethylamine. Triethanolamine, morpholine, tertiary amines.

The addition product neutralized with a base can be used as an emulsifying agent in the inventive emulsion polymerization of hydrophobic vinyl monomers with a Q value of at least 0.1, determined by the Qe scheme. The (2-f-scheme is a theory representing an addition reaction rate constant of a monomer with a radical, formulated by A 1 Frey and Price in 1947, and the "Q value" is a constant representing the general reactivity of the The constant e relates to the polarization effects of the substituent groups in the monomer (cf. GF D'Alelio AB "Fundamental Principles of Polymerization", pp. 432 to 437 , John Wiley & Sons Inc., New York, and Cheves Walling "Free Radicals in Solution", pp. 140 to 145, John Wiley & Sons Inc., New York) Examples of such vinyl monomers have the structural formula

CH ₂ = CCOOR ₂

R.

wherein R _{1 is} hydrogen or a methyl radical and R _{2 is} an alkyl radical having 1 to 18 carbon atoms. Examples of the vinyl monomers are alkyl esters of acrylic acid or methacrylic acid, glycidyl acrylate, glycidyl methacrylate, methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate, allyl acrylate, allyl methacrylate. Hydroxypropyl methacrylate, diethylaminoethyl methacrylate, allyloxyethyl acrylate, allyloxyethyl methacrylal, styrene, «-methylstyrene, vinyl toluene. Vinyl-

pyridine, butadiene, isoprene, chloroprene, acrylonitrile and methacrylonitrile - Preferred examples of vinyl monomers are alkyl (C ₂ - to Cg -esters of acrylic acid or methacrylic acid and siyrene. These vinyl monomers can be used alone or in admixture with one another. For example, as vinyl acetate with a Q value of less than 0.1 of the invention is subjected to emulsion polymerization using the specified emulsifier, the polymerization reaction of the vinyl monomer can not proceed effectively because the radical generated by the monomer is so active that it is easy with the used as an emulsifier maleinized butadiene polymer reacts. fs

In the invention, it is possible to use the hydrophobic vinyl monomers having a β value of at least 0.1 with less than 10 percent by weight, based on the above vinyl monomer, of water-soluble or to copolymerize hydrophilic other vinyl monomers. Examples of the latter are acrylic acid, Methacrylic acid, itaconic acid, acrylamide, N-methylacrylamide, N-ethylacrylamide, methacrylamide, dimethylaminoethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, N-methylol acrylamide butyl ether, 2-hydroxyethyl acetylate, 2-hydroxyethyl methacrylate. 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and acrolein.

According to the invention, the vinyl mopomer is maleinized in an aqueous medium in the presence of the Polymerized butadiene polymers as emulsifiers. This emulsifier is used in so'cher Amount used that the theoretical acid number, based on that in the vinyl polymer emulsion obtained total solids contained, ranges from 5 to 150. The »theoretical acid number, based on the total solid "is determined by the following equation:

(Theoretical acid number,

based on the total solid) = A

C. B.

led, which under the reaction conditions is higher than the freezing point of water, but lower than the boiling point of water. Stirring is preferred for the polymerization reaction, but it is possible to carry out the polymerization reaction without stirring, when the vinyl monomer emulsifies in an aqueous medium prior to the polymerization reaction will. Initiators to be used are, for example, organic or inorganic peroxides, sulfides, sulphonic acid, Sulfones, azo compounds, diazo compounds, nitroso compounds, persulfates, perchlorates, water- or oil-soluble redox initiators. In addition, actinic light, photosensitizers, electrical Irradiation, gamma rays, x-rays, and ultrasonic waves alone or in combination can be used with the above organic or inorganic initiators.

The polymer emulsion obtained according to the invention can have various additives depending on the Use of the emulsion can be added. If z. B. the emulsion as a carrier for paints can be used, dyes, plasticizers, extenders, dispersants, coalescing agents or other water-soluble polymers can be added to the emulsion. The polymer emulsion is also useful as an adhesive and resin treatment composition, and in such a case can optionally plasticizers, coalescing agents. Extenders and other vinyl monomers can be added

When the polymer emulsion is used as a vehicle for paint, the resulting paint can have various substrates can be applied by conventional coating methods such as Spraying, brushing and rolling. The applied film can be at room temperature or hardened at elevated temperatures.

In the following reference examples, the preparation of those used in the process of the invention is illustrated Addition products of butadiene polymer and maleic acid or its anhydride explained.

where A is the acid number of the maleinized butadiene polymer used, B is the total weight in grams of the maleinized butadiene polymer of the vinyl monomer introduced into the polymerization system and C is the weight in grams of the maleinized butadiene polymer which is fed to the polymerization system. If the amount of the emulsifier is too small to make the above theoretical acid value less than 5, the emulsion polymerization cannot proceed effectively. If the amount is so large that the theoretical acid value is over 150, the coating film obtained from the polymer emulsion tends to be poor in water resistance. The preferred amount of maleinized butadiene polymer used as emulsifier is such that the theoretical acid number, based on total solids, in the polymer emulsion obtained is in the range from 15 to 120.

The emulsion polymerization of the vinyl monomers can be carried out under the same conditions are, as in the usual emulsion polymerization, e.g. B. can emulsion polymerization in one aqueous medium with or without a radical initiator or with irradiation. The polymerization is carried out at a temperature from Reference Example 1

150 g polybutadiene with an average molecular weight of 1900 and consisting of 72% cis-1,4 bonds, 27% trans-1,4 bonds and 1% 1,2-vinyl bonds (hereinafter referred to as "polybutadiene A"), 20 g of maleic anhydride and 75 ml of xylene was placed in an autoclave and

in a nitrogen gas atmosphere by heating at 190 to 200 ° C. for 5 hours with vigorous stirring

implemented.

After the reaction, the obtained product was thoroughly washed with water. 60 ml ethylene glycol monobutyl ether (Butyl Cellosolve) was then added to the product and water was passed through a Evaporator removed therefrom leaving a maleinized polybutadiene solution. The received maleini-

υο sated polybutadiene had an acid number of 93, and the solution thereof had a concentration of 85.6% by weight.

Reference Examples 2 to 10

Predetermined amounts of polybutadiene A, maleic anhydride and xylene were added at a given rate

Temperature for a given period of time ¹ to produce maleinizable polybutadiene in the same manner as in Reference Example 1.

The amounts of the compounds, the reaction conditions and the properties of the products obtained are given in Table I.

Table I.

Output connections

Polybutadiene (g)

Maleic anhydride (g)
Xylene (ml)

Reaction conditions
Heating temperature

Heating time (hours) ...
solvent used

Methylcellosolve (ml)
Butylcellosolve (ml) ..

properties

Acid number

concentration
(Weight percent)

Reference example No.

2 j 3 4th 150 150 150 30th 45 12th 75 75 75 170-185 180-190 180-190 5 4th 5 50 60 60 76 116 49 76.3 76.4 83.5

173-186 5

150
30th
75

170-185

60

111
86.0

100
30th
50

170-185
4th

40

144
83.5

50
50
50

170-180

310
61.0

50 15 25

175185

20th

115 82.0

! 0

200

60

100

180-185

4.5

80

121 76.0

The products of Reference Examples 2, 3, 5, 9 and 10 removed. 80 ml of ethylene glycol monobutyl ether were

in Table 1 were obtained in the following manner. added to the precipitate and methanol was added

In Reference Example 8, methyl isobutyl ketone at 35 was removed from the mixture by an evaporator. Used in place of xylene.

In Reference Examples 2, 3 and 9

After the reaction, methanol was added to the product, and the mixture was left for 2 days left to make half esters. Ethylene glycol ether was added to the product, washed thoroughly with methanol was added, and methanol was removed from the resulting mixture by an evaporator.

In reference example 5

After the reaction, an excessive amount of diethylamine was added to the product, and the mixture was dissolved in methanol. The solution was then added to acetone to cause precipitation, and the precipitate was deposited and taken out. Ethylene glycol monoethyl ether was added to the deposited product. Acetone and methanol were removed from the mixture by an evaporator. In order to determine the acid number of the product, part of the sample was taken out after the reaction and added to methanol for precipitation. The product thus purified was used for the determination.

In reference example 10

After the reaction, the product was precipitated into methanol, and the supernatant became Reference Example 11

In the same manner as in Reference Example 1, 150 g of polybutadiene A, 15 g of maleic anhydride and 75 ml of xylene were ^{reacted at 175 to 185 °} C. for 4 hours and then cooled. The product was thoroughly washed with water and residual water was removed by an evaporator. The resulting maleinized butadiene polymer had an acid number of 89.6 and was free of water.

Reference example 12

In the same way as in Reference Example 1, 100 g of polybutadiene A. 30 g of maleic anhydride and 50 ml of xylene were reacted at 170 to 190 ° C. for 4 hours and then cooled. The obtained product was washed with water and then with methanol. A small amount of water was then added to the product, followed by removal of Metbano by an evaporator. The painted butadiene polymer obtained had an acid number of 140. This mixture contained 15.3 percent by weight of water.

Reference Examples 13 to 15

In the same manner as in Reference Example I, malemized butadiene polymer was prepared. Tuesday Quantities of the starting compounds a, the reaction! conditions and the characteristics of the reaction: Product are given in Table H.

509640/21

Table Il

Output connections
Polybutadiene A (g) ...
Polybutadiene B (g) ...
Polybutadiene C (g) ...
Maleic anhydride

(G)

Xylene (ml)

Methyl isobutyl ketone
(ml)

Reaction conditions
Heating temperature

C C)

Heating time (hours) ..
solvent used (butyl cellosolve,
ml)

properties

Acid number

concentration
(Weight percent) ...

Reference example No.

13th 14th 50 50 15th 50 25th 25th 25th 175180 173-180 4th 3 20th 20th 155 172 87.3 76.5

15th

100

50 50

20th

175-180 3

40

152 79.2 discarded. The obtained maleinized butadiene polymer contained 61.0 percent by weight water.

Reference example 17

30 g of the maleinized butadiene polymer solution prepared in Reference Example 6 was dissolved in methanol precipitated to remove ethylene glycol monobutyl ether. The obtained substance was each three times washed with water and methanol, and further washed thoroughly with methanol. After removing of the supernatant liquid, the remaining substance was reduced for 2 hours Print dried. The product obtained still contained about 50 percent by weight of methanol.

20th

In Reference Example 14 in Tables, the treatment was carried out after the reaction as follows. After cooling, 50 ml of glycerin were the Product added and the mixture allowed to stand overnight to form half-esters. The obtained product was washed with methanol and then ethylene glycol monobutyl ether was added was added to the washed product, after which the methanol was removed by an evaporator.

The polybutadienes B and C listed in Table II were structured as follows:

45

Polybutadiene B

Polybutadiene with an average molecular weight of 3,000 to 4,000. Consisting of 82.2% cis-1,4 bonds, 15.4% trans-1,4 bonds and 2.4% 1,2-vinyl bonds.

Polybutadiene C

Polybutadiene having average Einein Molekuiargewicht 1 300, consisting of 50% ice-1,4 bonds. 48% trans-1,4 bonds and 2% 1,2-vinyl bonds.

Reference example 16

60

The maleinized Batadienepolyraeriösung obtained in reference example 3 was in each case three times Washed water and nrit methanol. The washed * 5 The solution was then left to stand in water for 3 days. Bm water-soluble components completely into the water, and the water became Reference Example 18

50 g of polybutadiene A. 25 g of maleic acid and 25 ml of xylene were placed in an autoclave, which then has been closed. In the same manner as in Reference Example 1, the mixture was then under for 5 hours vigorous stirring to react at 190 to 225 ° C. Thoroughly with water and methanol 40 ml of ethylene glycol monobutyl ether were added to the washed product. A vaporizer became used to remove water and methanol. The substance obtained was precipitated again in water, washed thoroughly and left to stand in water for a day. Water was obtained to obtain a Mixture of maleinized butadiene polymer and water removed. The maleinized butadiene polymer had an acid number of 120 and a water content of 54.7 percent by weight.

Example 19

250 g of polybutadiene D (which had an average * molecular weight of 1420, with a terminal Carboxyl group with an acid number before 66.3 and consisting of 10.2% trans-1,4-linkers and 89.8% 1,2-vinyl bonds), 50 g maleic acid anhydnd, 60 ml of methyl isobutyl ketone and 150 ml of xylene were placed in an autoclave and poured into one Reacted nitrogen gas atmosphere by heating to 180 bis <190 C for 4 hours with vigorous stirring After the reaction, the obtained product was washed with water and then with methanol. 100 m Ethylene glycol monobutyl ether were used in the water Schenen product added, whereupon the methano by an evaporator to obtain a maleini Values Buiadienpolymerlösung was removed. There: maleinized butadiene polymers had an acid number of 39 and a concentration of 77.4 weight percent.

Convenience examples 20 to 23

In the same way as in reference example 19 maleinized butadiene polymer produced. Di quantities of the starting compounds, the reaction Conditions and properties of the products are * given in Table UI.

Tabel

Output connections

Polybutadiene D (g)

Polybutadiene E (g)

Polybutadiene F (g)

Polybutadiene G (g)

Maleic anhydride (g)

Xylene (ml)

Methyl isobutyl ketone (ml)

Reaction conditions

Heating temperature (C)

Heating time (hours)

solvent used (ethylene glycol

monobutyl ether)

properties

Acid number

Concentration (weight percent)

190 200

Reference example No.

21 22

50

50
50

175 185
4th

40

233
59

125

50 80 50

175 -185 4

50

162 92

300 180 200 150

185 195 4.5

120

190 83

Polybutadiene E, F and G in Table III were like is structured as follows:

Polybutadiene E

Polybutadiene with an average molecular weight of 1150 and consisting of 8.7% trans-1.4 bonds and 91.3% 1,2-vinyl bonds.

Polybutadiene F

Polybutadiene with an average molecular weight from 500 to 1000 with phenyl end groups and consisting of 10% cis-1,4 bonds. 45% trans-1,4 bonds and 45% 1,2 vinyl bonds.

Polybutadiene G

Polybutadiene with an average molecular weight of 1100 and consisting of 89.2% 1,2 vinyl bonds and 10.8% trans 1,4 bonds.

Example example 24

200 g polybutadiene H (with an average molecular weight of 4040 and consisting of 8% Eis-1.4 bonds and 92% U-vinyl bonds). 80 g Maleic anhydride. 100 ml methyl siobutyl ketone and 150 ml of xylene were placed in an autoclave and in a nitrogen gas atmosphere by heating at 185 to 195 ° C for 5 hours with vigorous stirring implemented. After the reaction, Ja's product was divided into two equal parts. Part got thorough washed with water and then precipitated in methanol. The other part was precipitated directly into methanol. 40 ml of ethylene glycol monobutyl ether were added to both parts, whereupon the methanoi was removed by an evaporator, to obtain malemized polybutadiene solutions. The former embodiment was referred to as Reference Example 24-1 and the latter as Reference Example 24-2. That The product of Reference Example 24-1 had an emc acid number of 130 and the solution concentration of 74% by weight, while the product of the Reference Example 24-2 had an acid number of 86 and a solution concentration of 80 percent by weight. 30th

Reference example 25

100 g of styrene-butadiene copolymer (with an average molecular weight of 2000 to 2400 and a content of 80% butadiene polymer and 70% 1,2-vinyl bonds), 100 g maleic anhydride. 100 ml of methyl isobutyl ketone and 150 ml of xylene were placed in an autoclave and ^{reacted in a stream of nitrogen gas with heating to 175 to 190 °} C. for 7 hours with vigorous stirring. After the reaction, the product was thoroughly washed with water and then precipitated into methanol. The supernatant liquid was removed and 40 ml of ethylene glycol monobutyl ether was added to the remaining substance. Removal of methanol with an evaporator gave a solution of maleinized butadiene copolymer. The copolymer had an acid number of 162 and a concentration of 89.5 percent by weight.

50 Reference example 26

200 g isobutylene-butadiene mixed polymer (mii an average molecular weight of 45 (up to 500. 3 to 4 unsaturated bonds per molecule and an iodine number of 150 to 180), 200 g of maleic acid anhydride. 100 ml of methyl isobutyl ketone and 150 m Xylene was placed in an autoclave and heated to 180 bi in a nitrogen gas atmosphere 190 C for 7 hours with vigorous stirring After the reaction, the product became clear washed with water. 80 ml Äthylengrykol-mono Butyl ether was then added to the washed product. After removing water only one Evaporator became a solution of maleimized egg Obadienmtschpolymerem obtained. The mixed pole; mere had an acid number of 116 and a Κόπτει tration of 87.2 percent by weight.

Reference Example 27 Cyclized polybutadiene having a molecular weight of KX) O to 1500 of the formula

CH ₇ -CH

CH

Il

CH ₂

CH ₂ -CH = CH-CH ₂ J - (- CH CH CH

CH ₂ CH CH

\ / \ / \ CH ₂ CH ₂

CH, CH ₂

1: 6: 15:25

was thoroughly washed with an aqueous 20 weight percent NaOH solution for one day in a nitrogen gas atmosphere, and further washed with water and methanol. The polybutadiene was then dried.

200 g of this substance, 200 g of maleic anhydride, 200 ml of methyl isobutyl ketone and 300 ml of xylene were placed in an autoclave and heated to 185 to 195 ° C in a nitrogen gas atmosphere Reacted for 5 hours with vigorous stirring. After the reaction, the product was thoroughly watered with water washed. 80 ml of ethylene glycol monobutyl ether were added to the washed product. By Removal of methanol with an evaporator gave a solution of maleinized butadiene polymer. The polymer possessed an acid number of 193 and a concentration of 81.7 percent by weight.

example 1

0.5 g of cobalt naphthenate and 2.0 g of lead naphthenate were dissolved in 71.5 g of butyl methacrylate. The resulting solution was placed in an autoclave together with 40 g of the maleinized polybutadiene obtained in Reference Example 1, 10 ml of 28% ammonia water, 100 ml of water and 200 mg of ammonium persulfate. The air in the autoclave was replaced with nitrogen gas by repeating the operation of alternate depressurization and nitrogen gas substitution for 30 minutes. The mixture was then ^{heated to 75 to 85 °} C. for 2 hours with stirring, whereby a polymer emulsion having a solids content of 47.8% was obtained. The particle size of the polymer in the emulsion was 0.14 to 0.18 microns and the theoretical acid number of the product was 30.0 assuming the butyl methacrylate was fully polymerized.

The obtained polymer emulsion was coated on a glass plate and kept at room temperature dried, whereby a transparent and hard coating was obtained. The coating showed so excellent water resistance that after hardening at room temperature for one day the Coating showed no change in the three hour water drop test.

The particle size measurement and the water drop test were carried out in the following manner:

Particle size

Visible rays of wavelengths 430 microns and 700 microns were irradiated on the polymer emulsion to be tested to reduce opacity and the particle size was determined by the method of Sakurade et al. published in Bull. Inst. Chem. Research (Kyoto Univ.), 42 (2-3), 145 (1964).

35

Water drop try

The polymer emulsion was applied to a glass plate and cured to form a cured one Coating film dried. A drop of water at room temperature was placed on the coating film applied to watch the changes in the film.

45

Examples 2 to 9

Polymer emulsions were prepared in the same manner as in Example 1, except that the polymerization was carried out under the conditions shown in Table IV below conditions shown has been carried out.

Table IV

Amount of used materials maleinized poly butadiene (g)

28% ammonia water

(mi)

Ml water)

30th

7th 100

Example no

J 4 j 5 J 6 Maleinized Batadicnpolymi used

2 f 3_ 4

; fan

30th

10
100

45

10 105 30

10
100

50

10
1IO

7th
ms

NrJ

20th

30th

10
inn

10
inn

15th

; ine itur irte igte learn the em

■ erus-

on; rng as in

continuation

16

Ammonium persulphate (mg) potassium persulphate (mg) «,« '- azobisisobutyro-

nitrile (mg)

Butyl methacrylate (g) ... cobalt naphthenate (g) lead naphthenate (g)

Polymerization conditions

Temperature ('C)

Time hrs.)

Properties solid content

(Weight percent)

Particle size (microns) acid number

Each polymer emulsion obtained in Examples 2 to 9 was coated on a glass plate and kept at room temperature cured, whereby a transparent and hard coating film was obtained. The ones from the Emulsions of Examples 2,4, 6, 7, 8 and 9 obtained coatings were one day after the coating subjected to the water drop test, but no change was found in the three hour test observed the respective coatings. Furthermore, from the emulsions of Examples 3 and

2
! 3
Vcrwcnd
6th <
clcs malcinisi
2 Ex
ertcs biitadie
3 ie! No.
6th
polymeric I.
4th 7th
in reference
19th 8th
spat! No.)
20th 200 200 100 200 200 _._ 100 71.5
0.5
2 71.5
0.5
2 71.5
0.5
1 71.5
0.5
2 71.5
0.5
2 200
71.5
0.5 71.5
0.2
2 70-85
2 60-75
2 53-70
2 80-90
3 70-80
2 60-70
2 60-70
3 47.5
0.14-0.16
24.6 47.3
0.08-0.10
29.3 45.3
0.28-0.34
24.6 44.8
0.14-0.20
28.1 48.1
0.32-0.40
18.3 45.0
0.23-0.27
22.0 46.1
0.06-0.08
38.3

24-1

100

71.5 0.2

65-75 3

42.0

<0.05

30.8

The coatings obtained were exposed to the same test 2 days and 7 days after coating, and no change was observed on the coatings in a three hour test.

Examples 10 to 20

Polymer emulsions were prepared in the same manner as in Example 1 except that Polymerization was carried out under the conditions shown in Table V below.

Table V

Amount of materials used, maleinized butadiene polymer (g | 28% ammonia water (ml)

Ml water)

Ammonium persulfal

(mg)

Potassium persulfate (mg) butyl methacrylate (g)

Polymerization conditions temperature (C) cell (hrs.)

Properties Solvent content (weight percent I. Particle size

(Micron)

Acid number

11th 12th 13th 9 Example no 14th 15th 16 14th 15th 17th 18th 24-1 IV 10 Used malcii 30th isicrtcs butadiene polymer (im 20th 30th Reference example ^ 30th 8th 8th 10 13th 10 20th 22nd 10 24-2 2 34 20th 100 30th 100 100 20th 100 40 30th 5 5 10 10 10 10 100 100 100 100 100 100 KX) 100 110 KX) KK) 71.5 80.5 71.5 71.5 _ 100 50 55-65 100 55-65 55-65 KX) 65-75 100 44.7 89.5 80.5 T ■ » 71.5 2 71.5 71.5 70 80 45-55 45.8 55-65 45.5 44.2 65-75 44.5 65-75 58-65 2 2 0.11-0.13 -f 0.19-0.21 0.40-0.48 2 0.30-0.48 2 I. 36.0 47.6 29.3 47.7 27.4 37.6 44.0 31.0 45.0 45.0 0.35-0.45 0.45-0.50 0.37-0.43 0.31-0.38 0.57-0.60 0.16-0.18 98.5 37.1 37.9 33.1 26.6 18.5

10 100

100

65-75 ι

0.48-0.50 44.3

In Example 19, the polymerization reaction was started by adding 5 ml of ethylene glycol monobut ether run to the system. , _,. ,,,

Transparent or hard coatings were obtained from the polymer emulsions of these examples. The water resistance of the coatings obtained from the emulsions of Examples JO, 16, 18 and 19 was excellent. In particular, the coatings of Examples 18 and 19 showed no changes 20 hour water drop test carried out on the coating film one day after coating became.

Examples 21-23

Polymer emulsions were prepared in the same manner as in Example 1 except that d.e Polymerization was carried out under the conditions shown in the following Table VI.

Table Vl Bet game no.

21

Amount of materials used

maleinized butadiene polymer (g)

28% ammonia water (ml)

Ml water)

potassium persulfate (mg)

Butyl methacrylate (g)

Polymerization conditions

Temperature ('C)

Time (hours)

properties

Solids content (percent by weight)

Particle size (microns)

Acid number

Examples 24 to 26

Polymer emulsions were prepared in the same manner as in Example 1 except that the Polymerization was carried out under the conditions shown in Table VII below.

Used maleinized butadiene 20th 20th 20th polymer (in example no.) 20th 30th 50 5 K) 15th 100 100 120 100 100 100 71.5 71.5 71.5 65-75 60 70 65 70 2 2 45.0 46.0 44.2 0.07 Ό, 08 0.15 0.16 0.30 0.36 28.0 38.7 54.5

Table VIl

Amount of materials used maleinized butadiene polymer (g)

Triethylamine (30 weight percent aqueous

Solution) (ml)

Ml water)

Potassium Persulfate (mg)

Butyl methacrylate (g)

Cobalt naphthenut (8%) (g)

Polymerization conditions

Temperature (C)

Time (hours)

properties
Solid content (percent by weight).

Particle size (microns)

Acid number

Example no.

I 25 I 26

Used maleinized Buladia

polymercs (in the reference example no.)

25th

30th

26th

30th

20th 15th 100 KK) 100 100 71.5 71.5 1 2 70 85 70 80 ■> 46.0 44.5 0.10 0.20 0.06 0.OX 44.3 31.2

30th

15 100 100

71.5

46.0

0.05 0.10 4'λ2

19th

Examples 27 to 35

20th

Polymer emulsions were prepared in the same manner as in Example 1 using various vinyl More oaomeric produced are given in Table VIII below. The polymerization conditions are also shown in Table VIII.

Table VIII

Amount of materials used
maleinized butadiene

polymer (g)

28% ammonia water (ml)

Water (mi)

Ammonium persulfate (mg) Potassium persulfate (mg) ..

Vinyl monomers and amounts

Acrylic acid (g)

Ethyl acrylate (g)

Butyl acrylate (g)

2-ethylhexyl acrylate (g) methyl methacrylate (g) .. Ethyl methacrylate (g) ... butyl methacrylate (g) ... lauryl methacrylate (g) ..

Acrylamide (g)

Acrylonitrile (g)

Styrene (g)

Vinyl toluene (g)

Isoprene (g)

Glycidyl methacrylate (g)

Polymerization conditions

Temperature (C)

Time (hours)

properties
Solids content

(Weight percent)

Particle size (microns)

Acid number

27

Example no.I 31 I 32

20th

100 200

67.2

50 to

43.0

0.48

until

0.50

20 ,: »

30th

10 100

50

8.2

65 to 70

47.0 0.11 to 0.13 33.7

10 40 30th 21 30th 10
100
100 10
100
100 25th ) 0
110
300 25.2 - 10
100
200 0.3
27 38.2 72 - 3
28 50 to 70
1 60 to 70
2 72 5 to 85
3 47.0
0.18
until
0.22
34.8 45.5
0.05
38.0 70 to 80
20 min. 38.0
0.30
until
0.35 42.0
0.50
until
0.60
48.4

3?
s (Bczugsbc
23 34
ispicl no.)
23 35
23 200 72 30th 66
737
3000 24
240
500 10
110
500 220 63
7.2 - 220 - 5 30th
30th 70 to 80
6th 56 to 75
2 70 to 85
5 41.0
0.50
until
0.60
52.0 40.0
0.60
until
0.70
57.0 34.0
0.60
until
0.70
56.0

In Examples 33 and 34, the depressurization process was not carried out before the polymerization reaction and in Examples 20 and 35, the depressurization process was shortened by 5 minutes. After the reaction, excess ammonia in Examples 29, 33 and 34 was evaporated removed, and in Example 35, excess ammonia and unreacted isoprene were removed.

Examples 36 to 41

Polymer emulsions were prepared in the same manner as in Example 1, with various in Neutralization millels indicated in Table IX were used. The reaction conditions are also in Table IX given.

Table IX

22nd

Amount of materials used
maleinized butadiene polymer (g)

Ml water)

Potassium Persulfate (mg)

Styrene (3)

Butyl acrylate (g)

Butyl methacrylate (g)

Neutralizing agent

Trimethylamine (30 weight percent

aqueous solution) (ml)

Triethylamine (ml)

Ethylamine (70 percent by weight

aqueous solution) (ml)

NaOH (g)

KOH (g)

Polymerization conditions

Temperature ('C)

Time (hours)

properties
Solids content (percent by weight)

Particle size (microns)

Acid number

Example no.

36 I 37 I 38 I 39 j 40 j 41

Maleinized structural polymer used (in reference example No.)

62.7

56
2

37.4

0.43-0.48
19.8

6th 6th 7th 30th 40 30th 100 110 100 100 100 100 40 43.6 40 32.4 28.8 32.4 4.5 - 6th 2.5 60 75 60 70 75 85 2 2 2 47.9 46.0 48.5 0.38-Ό, 46 0.11-0.13 0.20-0.22 29.3 35.9 27.1

30 100 100

71.5

15th

70 80 70

2 i 2

44.0

0.12-0.14

36.4

Examples 42 to 47

Polymer emulsions were prepared in the same manner as in Example 1, with various, in The following table X given radical initiators were used, with the proviso that in the examples 44 and 47 the polymerization was carried out in a stationary state in a glass vessel after the The starting mixture was thoroughly stirred. In Example 44, the polymerization was carried out at room temperature and carried out in example 47 in the glass vessel placed in ice water. The polymerization conditions are also given in Table X.

Table X

Amount of materials used
maleinized butadiene polymer (g)

28% ammonia water (ml)

Ml water)

Ethylene glycol monobutyl ether (ml) .. Ethylene glycol monomethyl ether (ml)

Butyl methacrylate (g)

Initiators

Sodium persulfate (mg)

FeCl ₃

30% hydrogen peroxide (ml)

α, α'-azobisisobutyl nitrile (mg)

Gamma rays (r / h)

Polymerization conditions
Temperature ( ⁰ C)

Time (hours)

"Example" NrT

42 I 43 I 44 I 45 | 46j 47

Maleinized butadiene polymer used (in reference example cl _Nf)

19th

71.5

0.16
1.0

50-65

Il 12 13th 20/20 4th 20th 1 100 12th 20th 62.7 7.2 100 - - 2.5 · 10 ⁴ 70-80 room temperature 2 Ίο

19th

100

71.5

200

70-80

30th

100

71.5 100

55-65

2.5 x 10 "

continuation

24

Solid content (percent by weight). Particle Size (microns)

Acid number

Ucnpid No.

j 43 I 44 I 45 | 46j 47

Vet wendel «, maleintucmt BuUutieupolyineres (in He / ugsbetspiel no.)

45.0 <Q.Q5

12th Il 12 11th 4S, 0 19th 45.5 40.9 42.2 03 0.35 45jO 0.24 0.28 0.20 0.25 036 0.42 22jO 0.23 0.28 45.0 41.7 50.7 22.0

Examples 48 to

Polymer emulsions were prepared on the same fabric as in Example I, except that the Polymerization was carried out under the conditions given in Table Xl below.

Table Xl Amount of materials used

maleinized butadiene polymer (g)

28% igcs ammonia water (ml)

Ml water)

Athyienglykol-monobutyiäthcr (g & .. Butyl methacrylal (mg) Ammonium persuUate (g) Cobalt naphthenate (g) Blet naphthenate (g) Polymerization conditions Temperature ("C)

Time)

properties Solid content (percent by weight). . Parükdnsize (microns)

Acid number

*} The entire amount <ks in the reference tbeapki 17 erfaahenea Prodi **

Example SI

In an autoclave, 30 g of the ecn Polybatadiea obtained in the example,! OH sol water, 7 to 28% ABewnsakwasser, 713 g Betyfanetfeacryiat, O ^ g Koba MflaptilfaaMt, 0.1 ai TOgi wii 1ilmm »r nfipr a Waseento ^ paBoMd $ QjIKg Bseochlorid Dgebru- The UA m the Aotokiav is replaced by aal SüdatoBgas, «ad d»

16
60

10 80

71.5 200 0.5 2JO

75 2

42.9

0.18 O ^ 2 28.6

BcHfMClNr. 49

Butju £ iciipofjrmeres (in Benigsbeisp »d no.)

17th *)

10 105

71.5 200 0.5 2JO

70

43.4

0 32 29.3

10 WQ

62.7 200

60 70

34.0

0.12 0.14 7/31

tae

no change after 3 ^ hours of water droplet versacfa

Each in dea Betspieka IO to SO erbatteae Potymcrenmtew was on glass plates on% ettag? N and at Zmunerteapenttw dried Somü will firmly £ ecteft that every i in dit * cu Beeptclca. Betspielee 2S, 31, 32 and 38,

0Dq hSQFcCQ BpCSHsft ^ wftlKDttSBBwtt

g ca 28, si, 92 became * »ba chbct cdUHiCB " tcatpemues wob

des SfSteaM anf 3T ¹ C afaSfaL Die

■ ad die Partioefaig röBc des P o tyactra bctrwgOJ 2 bb

CLS6 A ^ 9onOflL THE flpDOCCbBChC SsHBCSESBlt DCSBO

die goaaaeo Fatetofc dor rwidiinn, bet rog Zadoaiadea 37.40 wad 45 t » m

23

tar I Woebebaggcuockaet The Btind

mF

The gloss, hardness and water resistance of the coating film were determined by the following Method measured to give the results shown in Table XII below. In Table XII, the properties of the on are the same Manner as above obtained from commercially available acrylic polymer emulsion coating film for the purpose of the comparison is also given.

Mirror finish:
ASTM D-523-62T, 60.

Hardness:

The pencil hardness was dried on each

Coating film was measured for a predetermined period of time shown in Table XII.
Water resistance:

On the predetermined one specified in Table XII A drop of water was applied to the dried coating film, and the film was allowed to stand at a relative humidity of 100%. The water resistance was taken as the time it took to create bubbles on the coating expressed.

shine hardness !Day Table XII hardness water
placidity hardness (Days 7 days hardness water
resistance example (60 C) 4B Water
Responsibility 2 days HB 12 hours HB water
resistant wedge F. 24 hours No. 63 4 hours 20 hours I. 3B 30 min. HB > 10 hours HB F. > 2 days 59 5 hours > 24 hours 2 <6B 10 min. 3B 4 hours B. HB > 9h 74 I hour 30 min. > 6h 3 2 B 50 min. HB > 10 hours HB F. > 24 hours 61 3B 4 hours B. IStd. HB > 24 hours F. 3 hours. 4th 73 * 30 min. 30 min. 2 hours. 30 min. 5 6B B. > 24 hours HB B. > 6 days 63 3B > 12 hours 3B 3 B > 4 days 2 B 6th 66 <6B > 24 hours 4B 4B 2 B ... 7th 75 3B 20 hours 2 B 2 B B. 8th 88 2 B > 24 hours B. B. B. 9 70 3B > 24 hours B. B. B. 18th 60 3B > 24 hours 3B 3B 2 B 19th 88 4B > 24 hours 3B 3B 3 B 21 78 3B > 24 hours 3B 3B 3 B 22nd 73 20 hours B. B. 23 80 2 B 2 B 24 75 B. HB 25th 73 3B 2 B 17 min. HB HB 2 hours. 26th 72 4B 10 min. 4B 4B 35 min. 3 B 37 79 3B 10 hours 3B 3B 3 B 40 73 3B > 24 hours 3B 3B 3 B 45 69 3B > 24 hours 3B 3B 3B 46 75 4B > 24 hours B. 41MiiL > HB HB 3 hours. 47 78 12 min. 2 hours. 3QMm. 48 6B 2 B 7 hours B. HB > 24pcs 72 3B 3 hours. 3B ? Mht 3B > 15SKL 3B 40Μΐη. 49 51 7mm. 14 min. Vergiach

Claims (1)

Patent claims: with a ρ-value, determined according to the g-f scheme. I. Process for the polymers of vinyl monomers in aqueous media using an emulsifying agent, characterized in that a vinyl monomer with a value determined according to the e-scheme of at least 0.1 and as an emulsifying agent an addition product neutralized with a base, o a butadiene polymer with an average molecular weight of 200 to 40,000 and at least one of the compounds maleic acid and its anhydride are used, the addition product having an acid number of 20 to 350.5 and being added to the polymerization system in such an amount that the theoretical acid number is based on the total solids contained in the resulting polymer emulsion is in the range of 5 to 150 f ^ Sah'n nach Änsprlch ^., characterized in that the addition product is added to the polymerization system in such an amount that the theoretical acid number, based on the total _{solids contained in the polymer emulsion obtained, is in the range from 15 to 1201ieet}