DE1219227B - Process for the preparation of water-insoluble linear addition polymers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08f

German class: 39 c -25/01

Number: 1 219 227

File number: R 27704IV d / 39 c

Filing date: April 6, 1960

Opening day: June 16, 1966

It is known that polymethyl methacrylate because of its durability and resistance is an excellent coating material to ultraviolet light. It's been outdoors for a long time durable without cracks or discoloration being observed. Shine and color in particular are retained pigmented polymethyl methacrylate obtained. Since it is quite hard and stiff, the polymethyl methacrylate is suitable especially for covering stiff substrates.

For substrates that require a softer, more flexible coating material, such as paper, textiles or Leather, a smaller amount of methyl methacrylate is mixed with a larger amount of one or more acrylic acid esters copolymerized or completely by one or more polymeric esters of acrylic acid replaced. These mono- or copolymers of acrylic acid esters are with or without methyl methacrylate Resistant to ultraviolet light if the acrylic acid ester content largely consists of esters Alcohols containing at least 4 and preferably 8 to 18 carbon atoms. With that easy Accessible methyl and ethyl acrylate as the main component of these copolymers is resistance however, little to ultraviolet light. This disadvantage particularly affects when using it in pigment printing and pigment dyeing of textiles that are often washed and exposed to sunlight get abandoned. By destroying the polymeric binder and washing out the binder and the pigment progressively fades.

There has now been a process for preparing water-insoluble linear addition polymers by polymerization a mixture of

a) at least 50 percent by weight of a methyl or ethyl ester of an α, ^ - olefinically unsaturated Monocarboxylic acid,

b) 3 to 50 percent by weight vinyl toluene,

c) optionally up to 47 percent by weight of one or more other copolymerizable ones monoolefinic compounds and

d) optionally 1 to 10 percent by weight of copolymerizable monoolefinic compounds found with functional groups in the presence of a free radical forming catalyst, in which the copolymers are then soft and nonetheless resistant to ultraviolet light arise when the methyl or ethyl ester of a «, ^ - olefinically unsaturated monocarboxylic acid the esters of acrylic acid are used.

Process for the production of water-insoluble
linear addition polymer

Applicant:

Rohm & Haas Company,

Philadelphia, Pa. (V. St. A.)

Representative:

Dr. W. Beil, A. Hoeppener and Dr. H. J. Wolff,

Lawyers,

Frankfurt / M.-Höchst, Adelonstr. 58

Named as inventor:

John Kucsan, Philadelphia, Pa .;

Benjamin Berryl Kine, Elkins Park, Pa. (V. St. A.)

Claimed priority:

V. St. v. America April 21, 1959 (807 762)

Processes for the production of copolymers from an alkyl ester of an - - olefinically unsaturated monocarboxylic acid, vinyl toluene and other copolymerizable mono-olefinic compounds, namely acrylic acid, methacrylic acid, fumaric acid di and fumaric acid monoalkyl esters and maleic acid monoalkyl esters, are already known from the US Pat. No. 2,851,448. In the production of these copolymers, however, the alkyl ester of a <x, β- olefinically unsaturated carboxylic acid used is not the methyl or ethyl ester of acrylic acid, but a different alkyl ester of methacrylic acid.

The vinyl toluene can be pure o-methylstyrene, trade m-methylstyrene or p-methylstyrene, however, mixtures of two or more of these isomers can also be used. The im The following expression used vinyltoluene denotes a commercially available product, in addition to o- and m-methylstyrene contains mainly p-methylstyrene.

The mixed polymerization with only 3 percent by weight of vinyl toluene improves the resistance to Ultraviolet light noticeable, even if the polymer contains substantial amounts of one or more of the contains the following compounds: methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate or acrylates Alcohols containing 4 to 18 or more carbon atoms. For most practical purposes, min-

609 579/420

3 4

at least 10 weight percent vinyl toluene is used. Emulsifier can be between 1 and 6% based

The preferred range is between about 15 and 15 based on the total weight of the monomers.

50 weight percent vinyl toluene. With these amounts the polymerization temperature can be between 0 and

is about 100 ° C, preferably between 30 and 80 ° C, without the use of higher acrylic acid esters,

already achieved resistance to UV light. 5 lie. The easiest way to do this is at room temperature.

This stabilization of copolymers from door without the application of external heat from the to

at least 50 percent by weight of ethyl or methyl polymerizing monomers and the redox

acrylate creates an emulsion against ultraviolet light through a mixing system. The amount of catalyst

Polymerization with 3 to 50 weight percent vinyl can vary, but is best between 0.01

toluene is surprising because homopolymers of i ° and 3% peroxide, based on the weight of the

p-Methylstyrene as well as styrene is a special monomer. The reducing agents are similar

Require stabilization against sunlight (see USA. - or smaller amounts recommended. So it is

Patent Specification 2,732,366). The copolymer can be used to prepare dispersions that are only 1 ° / ₀ to

also up to 47% of one or more other mixed- up to 60 percent by weight or even more mixed-

polymerizable, monoolefinic compounds contain polymerizate. Preferably dispersing

hold, e.g., methyl, ethyl or butyl methacrylate, sions that are about 30 to 50% solids

as well as other esters of methacrylic acid with others.

Alcohols containing 3 to 18 carbon atoms, Solvent polymerization can be carried out in toluene,

also acrylonitrile, methacrylonitrile, vinyl acetate, styrene, xylene, n-butanol, cyclohexanol, dimethylformamide

Acrylic esters with alcohols containing 3 to 18 carbons or mixtures of these solvents

contain material atoms, vinyl chloride and vinylidene are

chloride. The from according to the process according to the invention

Optionally, the copolymer can also be prepared from addition polymers obtainable over about 1 to 10 percent by weight of copolymerizable, monoolefinic compounds with functional compounds are resistant to ultraviolet light and can contain the sun groups without being damaged. These functional groups are exposed to light. Furthermore, they can serve various purposes. You can draw mechanical stability and the ability to e.g. B. Reactivity to crosslinking auxiliaries to absorb large amounts of pigments. Average their stability, such as aliphatic and aromatic polyiso- is not affected by this,
give cyanates, polyepoxides and aminoplasts. 30 The copolymer dispersions can be given examples of such monomers: Acids, such as diluted with water and then directly to acrylic acid, methacrylic acid and itaconic acid; Amides, coating of paper, leather, textiles, ceramics and such as acrylamide, methacrylamide, N-Methylohnethacryl- Metals, which are either bare or primed with commercially available amide, N-methoxymethyl methacrylamide, N-methyl lacquers, are used. Another acrylamide, / S-ureidoethyl acrylate or methacrylate and 35 possibility of application consists in melting the β- ureido isobutyl vinyl ether or sulfide; Amines, copolymers and application of the still hot like / I-Aminoäthylvinyläther, ιβ-Ammoäthylvinylsulfid, mass on the appropriate substrates.
/ S-dimethylaminoethyl acrylate or methacrylate, 4-VI The copolymers, prepared according to the vernylpyridine, 2-vinylpyridine and 2-methyl-5-vinylpyr- drive according to the invention, are also suitable for idin; Alcohols, such as β-oxethyl acrylate, methacrylate, 40 application of waterproof coatings to stones, cement, vinyl ether or vinyl sulfide and / S-methacryloxy concrete, bricks, roof tiles made from asbestos cement and acetamidoethyl-N, N'-ethylene urea. other masonry usually exposed to moisture

The interpolymerization can by block, are exposed.

Solvent, emulsion or suspension polymer- The aqueous dispersions obtainable according to the invention

sation can be achieved and is in the presence of a 45 ion or solutions of the copolymers in

free radical forming catalyst, e.g. B. organic solvents result in clearer form

niche or inorganic peroxides or with masses thin, clear, shiny, transparent and

Peroxy or azo compounds carried out. These very decorative covers.

Substances can be used in an amount of 0.1 to 3%, based on The copolymers are suitable for stabilization on the total weight of the monomers, or even in 50 of woolen fabrics against shrinkage during washing, as larger amount can be used. Preferably used as a binder for nonwoven fabrics and as a base 0.5 to 1%> to obtain a high molecular coating for various tissues, e.g. B. Velvet fabric to achieve weight. The molecular weight of the mixed and especially for carpets. You lend the Polymerisate can have between 10,000 and several tissues fullness and prevent fraying. In Millions lie and z. B. 5,000,000 to 10,000,000 55 of their properties as binders for non-woven fabrics be. Substances are the process products of the polymer

For the emulsion polymerization it is advantageous to use sation products from acrylic acid alkyl esters with 5 to a redox system. The action of the redox carbon atoms in the alkyl group, acrylonitrile system can be controlled by using a chain regulator, or alkyl acrylonitrile and other monoolefi such as mercaptoethanol or another mercaptan, 60 niche monomers according to the British patent. These chain regulators can also be far superior in writing 773 427.
Compound with the peroxide and azo catalysts can be used according to the invention with 1 to 10% copolymerization. The use of an anionic, barren monoolefinic compound with functional ionic or cationic emulsifying agents or copolymers produced by small groups, which support a mixture of these emulsifying agents which are heat-curable, are suitable as binders for polymerization. They can also be used for pigment printing and pigment dyeing for textiles. Dispersion of the copolymer after completion The following examples, in which the indicated polymerization stabilize. The amount of parts required and the percentages, if not

otherwise noted, based on weight, 10 parts of vinyltoluene and 2 parts of itaconic acid illustrate one the method according to the invention. aqueous dispersion of a copolymer prepared. After cooling, sodium hydroxide solution was neutralized to pH 7.1 with dilute Example 1.

5 To prove the good lightfastness

By emulsion copolymerization at 60 ⁰ C 11 parts of this dispersion with 2.5 parts of a blue was from 88 parts of ethyl acrylate, 10 parts of vinyl copper phthalocyanine pigment, 5 parts of a 1% strength toluene and 2 parts of itaconic acid in 200 parts of water aqueous solution of tert. Octylphenoxypolyäthoxyin the presence of 0.5 parts of ammonium persulfate ethanol, 15 parts of sodium alginate (0.5% aqueous and 0.5 parts of sodium hydrosulfite and 3 parts of io solution) and water to fill 300 cm ^{3 of} an ethylene oxide condensate of a tert. Octylphenols mixed and adjusted with ammonium hydroxide to pH 8 with 40 oxyethylene units per molecule, which is adjusted to 9.

one side as an emulsifier and on the other a sample of 80 x 80 cotton percale was used with

Treated side as a dispersant for the formed mixing of the color mass. Then it was served in a polymer, an aqueous dispersion of a 15 frame stretched, mixed polymer prepared for 5 minutes at room temperature. The Reaktionstempera- dried and then 10 minutes at 150 ⁰ C door of 6O ⁰ C was maintained for 3 to 4 hours. heated.

Then, while stirring, 13 parts of a methyl This sample was compared with a sample,

methacrylate monomers added. ^{1 and} ₂ hours later, which had been prepared in the same way, 0.14 part of potassium persulfate and then 0.16 part of ao copolymer, but instead of the vinyl toluene, sodium bisulfite was added. Contained methyl methacrylate. Every pattern was

Put in a fadeometer for 50 hours and then

Example 2 subjected to a complete Sanforize wash. That

Samples containing vinyl toluene retained 64% of its

From 85.5 parts of ethyl acrylate, 12 parts of vinyl toluene, 25 initial color, while the methyl methacrylate 1.14 parts methacrylamide and 1.36 parts methylol-containing sample only 7% of its initial color methacrylamide in 200 parts of water was retained.

Emulsion polymerization at 6O ⁰ C in the presence of B bis ρ ie 1 5

0.5 part of ammonium persulfate and 0.5 part of sodium

umhydrosulfit using 3 parts of a 30 Following the procedure of Example 2 was from Äthylenoxydkondensats a tert. Octylphenol with 88 parts of ethyl acrylate, 10 parts of vinyl toluene and 40 Oxyläthyleneinheiten per molecule as an emulsifying agent 2 parts of itaconic acid by emulsion polymerization an aqueous dispersion of a copolymer at 6O ⁰ C, an aqueous dispersion of a Mischpolyhergestellt. The temperature of 6O ⁰ C was 3 to merisats produced.

Maintained for 4 hours. 35 To demonstrate advantageous properties was

after completion of the polymerization with dilute

Example 3 Sodium hydroxide solution neutralized to pH 7.1, with 300 parts

Water dilutes and the mixture on one not

Following the procedure of Example 2, a woven fabric made from three superimposed 53 parts of ethyl acrylate, 45 parts of vinyl toluene and 40 carded webs of cotton fibers was sprayed into 2 parts of methacrylamide as an aqueous dispersion. The sprayed fabric was made of 10-minute emulsion copolymer. This manufacturing th at 140 ⁰ C dried pushed together to the fibers and bind at 100 ⁰ C quickly dried coatings. A durable, flexible product was obtained that was not resistant to oils and fats of all kinds. They yellowed, fibrous product that repelled ultraviolet water, did not accept dirt, and did not discolour light and stresses caused by washing was.
Exposed to sunlight. Similar fibrous products were made with a

To demonstrate advantageous properties, a copolymer of 98% ethyl acrylate and 2% was used to create a series of asbestos cement panels with an itaconic acid and a copolymer of 88% mixture of 40 parts of the 50 ethyl acrylate prepared according to Example 2, 2% itaconic acid and 10% styrene polymeric dispersion, 10 parts bound according to Example 3. Thereafter, the products were exposed to polymeric dispersion prepared for 25 hours and exposed to ultraviolet light for 10 parts. The vinyl toluene water sprayed. 16.5 to 27.5 g of solid resin mixed polymer product were increasingly applied per square meter of solvents. The panels medium-resistant, if it was in a mixture of the same, were then dried at 95 ° C for 16 hours. The 55 parts of toluene and methyl isobutyl ketone examined such coated plates can be up to a height. After 25 hours it was only slightly swollen from 0.60 to 0.90 m stacked without one and was still washable while the other sticking occurred. They repel water and copolymer products remain essentially unchanged during irradiation, even in the open air. They soften considerably in the solvent and do not show any deposits during washing and do not discolor completely after 25 hours of ultraviolet radiation, while roof tiles without a coating or roofing resulted in disintegration of the fabric, tiles with a coating containing styrene dirty
and got a little lighter in color. Example6

Example ^{4 6} 5 Following the procedure of Example 2 was carried out by

Emulsion polymerization from 75 parts of ethyl acrylate,

Following the 'procedure of Example 2, 10.5 parts of vinyl toluene and 12 parts of 2-ethylhexyl acrylate were added Emulsion polymerization from 88 parts of ethyl acrylate and 2.5 parts of itaconic acid, an aqueous dispersion

Example 7

ok

a copolymer produced. To demonstrate superior properties, a coating from 5 percent by weight of this copolymer, 0.5% of a blue copper phthalocyanine pigment, 0.11% Ammonia, 0.05% of an ethylene oxide condensate of tert. Octylphenol with about 10 oxyethylene units each Molecule, 0.075% sodium alginate and 0.20% 2-methyl-2-aminopropanol-1-hydrochloride used. The pH had previously been adjusted to about 8.5 with ammonium hydroxide.

A piece of 80 x 80 cotton fabric was run through the pigment dispersion and then through two nip rolls. It was then hung in a frame and air dried for 5 minutes. It was then heated ^{to 150 °} C. for a further 10 minutes. The fabric remained soft and pliable and showed good resistance to the stresses of any washing (it was tested by washing in 0.1% sodium stearate at 80 ° C. for 40 minutes with a spin and rinsing several times in water for 10 minutes). It was resistant to chemical cleaning with perehloroethylene, practically rub-resistant and remained essentially unchanged during washing even if the fabric was exposed to ultraviolet light (tested according to the so-called "cyclic aging test", exposure to ultraviolet light in a fade meter for 50 hours and subsequent washing test in the manner indicated above).

With a copolymer of 15% vinyl toluene, 5% methacrylamide and 80% methyl acrylate was get a similar result. The impregnated fabric was particularly resistant in the cyclical aging test.

With a copolymer containing 10.5 parts of methyl methacrylate instead of vinyl toluene, After 50 hours of irradiation with ultraviolet light during washing, a large part of the disappeared Colour.

30th

35

40

Following the procedure of Example 2, about 10% vinyl toluene, about 87.5% ethyl acrylate and about 2.5% itaconic acid produced an emulsion copolymer.

Example 8

Example 1 was repeated with the difference that the ethyl acrylate was replaced by 88 parts of methyl acrylate was replaced.

Example 9

From 45 parts of vinyl toluene, 202.5 parts of ethyl acrylate, 45 parts of methyl methacrylate and 7.5 parts ß-Methacryloxyacetamidoethyl-N ^ '- ethylene urea, in 350 parts of water by means of 9 parts of an ethylene oxide condensate a tert. Octylphenol was emulsified with 40 oxyethylene units per molecule, was in The presence of 1.5 parts of ammonium persulfate and 1.5 parts of sodium hydrosulfite at 60 ° C. is an emulsion copolymer manufactured. The reaction temperature was held at 60 ° C. for 3 to 4 hours.

Example 10

Using the procedures outlined in Example 1, the following monomers were also obtained Mixed polymers produced:

1. 12% vinyl toluene,
83% ethyl acrylate,
10% vinyl acetate.

2. 15% vinyl toluene,
50% ethyl acrylate,
25% methyl acrylate,
10% styrene.

3. 20% vinyl toluene,
66% ethyl acrylate,
10% acrylonitrile,

2% methacrylic acid,
2% N-methylol acrylamide.

4. 15% vinyl toluene,
50% methyl acrylate,
25% methyl methacrylate,

10% / S-hydroxyethyl methacrylate.

5. 12% vinyl toluene,
50% ethyl acrylate,

5% 4-vinylpyridine,
33% butyl methacrylate.

6. 5% vinyl toluene,
65% ethyl acrylate,
25% methyl methacrylate,

2% acrylic acid,

3% N- [| S-a-methacryloxyacetamido] ethyl -] - N, N'-ethylene urea.

Claims (2)

Patent claims: 1. Process for the preparation of water-insoluble linear addition polymers by polymerization a mixture of a) at least 50 percent by weight of a methyl or ethyl ester of a «, ^ - olefinically unsaturated Monocarboxylic acid, b) 3 to 50 percent by weight vinyl toluene, c) optionally up to 47 percent by weight of one or more other copolymerizable ones monoolefinic compounds and d) optionally 1 to 10 percent by weight of copolymerizable, monoolefinic compounds with functional groups in the presence of a free radical forming catalyst, characterized in that the methyl or ethyl ester is a «, ^ - olefinically unsaturated Monocarboxylic acid, the esters of acrylic acid are used. 2. The method according to claim 1, characterized in that the copolymerization in one aqueous medium containing an emulsifier is carried out. References contemplated: U.S. Patent No. 2,851,448; British Patent No. 773 427.