DE1022799B - Process for the production of polymers and copolymers - Google Patents

Description

One already has the production of polymerizable isocyanate esters of acrylic, methacrylic, α-chloroacrylic and Crotonic acid all the general formula

Ζ —COO —A —NCO

in which A is an alkylene group CjjH ^ j with η as an integer from 2 to 14 inclusive and Z is one of the groups CH ₂ = CH-; CH ₂ = C (CH ₃₎ -; CH ₂ = C (Cl) -; and CH ₃ - CH = CH - are proposed. The present invention relates to the preparation of the polymers of these isocyanate esters and their copolymers with other copolymerizable compounds which _{contain at least one vinylidene group, CH 2} = C <.

Esters of the above general formula suffer, especially in the presence of a free radical Catalyst, addition polymerization with the formation of soluble, thermoplastic, resin-like polymers of high molecular weight with 2 or more reactive isocyanate groups.

The products are of commercial importance, especially since the isocyanate groups present in the polymers in turn can react with compounds that z. B. amino, hydroxyl, mercapto and carboxyl groups with contain reactive hydrogen atoms. In this way, a variety of substituent groups can be attached The resinous molecules of the products of the process are added together, increasing the possible applications these polymers enlarge. Furthermore, the isocyanate groups in the polymers react with the Hydroxyl or amino groups of carbohydrates, which include cellulose compounds, or of protein-like ones Substances, e.g. B. proteins as such and wool. The isocyanate esters are used in this way to Cross-linking the molecules, thereby changing the physical and chemical properties of the carbohydrates and of protein-like substances change considerably. So wool is easily changed and treated with the polymeric isocyanate esters of the invention made very resistant to shrinkage, since over the Isocyanate groups between the polymer and the wool a real chemical reaction takes place through which the wool and the polymer are chemically bonded to one another.

The polymeric isocyanate esters not only serve as crosslinking agents for other, two or more reactive ones Substances containing hydrogen atoms. You can also be self-connected and practical in this way made insoluble and infusible. For this purpose, there are two or more active hydrogen atoms containing compounds, e.g. B. polyamines, polyhydric alcohols, amino alcohols and polycarboxylic acids, used. Examples of such compounds are ethylenediamine, diethylenetriamine, triethylenetetramine,

for the production of polymers
and copolymers

Applicant:

Rohm & Haas Company, Philadelphia, Pa. (V. St. A.)

Representative: Dr.-Ing. Dr. jur. H. Mediger, patent attorney, * 5 Munich 9, Aggensteinstr. 13th

Claimed priority:
V. St. v. America November 8, 1962

Newman Mayer Bortnick, Oreland, Pa. (V. St. A.), has been named as the inventor

Ethylene glycol, polyethylene glycols, e.g. B. triethylene glycol, glycerin, pentaerythritol, sorbitol, mannitol, oxal

acid, adipic acid, ethanolamine, diethanolamine and propanolamine. The polymeric isocyanate esters react also with the free hydroxyl or carboxyl groups of alkyd resins, creating new crosslinked products.

The polymerization of the monomeric isocyanate esters of the invention either on their own or in mixtures with each other or in copolymerizable mixtures with other types of copolymerizable, at least compounds containing a vinylidene group, CH = C <, can be carried out in bulk or in solution will. It can also be those isocyanate esters that have a tertiary carbon atom on the isocyanate group, are polymerized in aqueous emulsion due to their unusual resistance.

The products of the invention can be used with a large number of compounds containing a vinylidene group contain, are copolymerized. However, since the isocyanate groups are reactive, one must not apply such polymerizable unsaturated compounds that are reactive hydroxyl, amino or Contain carboxyl groups if you get a soluble, linear, thermoplastic copolymer wishes. Examples of copolymerizable substances with the isocyanate esters according to the invention

709 849/436

thermoplastic copolymers are: N-dialkylacrylamides, z. B. dimethylacrylamide and Diethylacrylamide; the alkyl esters of acrylic, α-chloroacrylic and methacrylic acid, e.g. B. methyl acrylate, octyl acrylate, Ethyl methacrylate, methyl methacrylate, butyl chloroacrylate and lauryl chloroacrylate; Styrene, α-methyl styrene and vinyl naphthalene; Vinyl chloride and vinylidene chloride; Allyl and methallyl esters of saturated aliphatic Carboxylic acids, e.g. B. allyl acetate and methallyl

The mixed polymer was solid, smelled of monomers and was soluble in toluene. After heating to 110 ^{D for a} further 1 hour, the copolymer no longer dissolved in toluene, but swelled eight-fold when it was immersed in toluene. After heating for a further 3 hours at 180 ° ^C. , the cast body obtained was insoluble and infusible, extremely clear, possessed a considerably greater abrasion resistance and resistance to the formation of hairline cracks and a higher degree of heat deformation.

of stearyl and cetyl alcohol mixture and 0.05 percent by weight of azoisobutyronitrile and 200 parts of benzene was refluxed for 24 hours. By measurement of the solid particles, a yield of 98 ° / ₀ of copolymer resulted.

propionate; Acrylonitrile; Vinylpyridine and the like important ίο temperature than one made of methyl methacrylate alone What is important here is that copolymers are produced under the same conditions as cast bodies produced, can, the two or more reactive isocyanate

groups contained in each macromolecule; that the number example 3

such reactive isocyanate groups are varied A mixture of 20 parts / j-Isocyanatäthylmeth-

can by varying the proportions of the isocyanate ester and the 15 acrylate, 80 parts acrylic acid ester of stearyl copolymerizable compound, and that
the polymer can be crosslinked and made insoluble
can and thus the properties of a thermosetting resin by reaction with a compound

acquires which contains two or more groups that, like 20 The solution was given on a piece of tanned leather, described above, react with isocyanate groups. Or the leather was dried in an oven at 65 ° and the isocyanate groups in the copolymer can be subjected to a bending test during cooling, in which the sowed with reactive groups in protein-like associations a coated side of the leather in contact with water bindings, e.g. B. glue or wool, are implemented. Several thousand bends were required as a result of which they combine chemically with the latter and before a slight wetting of the other side of the leather is established Protein-like compounds could be put in their properties. A homopolymer made from acrylic is significant be modified. acid esters of stearyl and cetyl alcohol mixture alone,

The isocyanate esters of the invention can be prepared and tested in the same manner as above mentioned substances in all proportions was far less permanent or free-polymerized will; the respective ratio of the 30 digend.

monomeric components that one chooses depends on -d ■. ,,

the end use of the copolymer.

It seems expedient that at least 0.2 and preferably a mixture of 3 parts / 3-isocyanate ethyl methacrylate,

wise 1 to 50 percent by weight of the isocyanate ester to 97 parts of methyl methacrylate, 1 part of azoisobutyronitrile Preparation of the copolymers then applied 35 and 200 parts of "Cellosolve" acetate was applied for 24 hours should be heated when the presence of two or more 85 °. The resulting viscous solution was on glass reactive isocyanate groups in the Makromole- applied and heated to 200 ° for 30 minutes. The one with it Cooling the final copolymer ensures the resulting film was not attacked when it was touched shall be. immersed in toluene at 25 ° for 24 hours. At the

The polymerization or copolymerization of the invention was heated in toluene to 50 to 60 ° overnight, the swelled The ester according to the invention is threefold with heat, ultraviolet clear film, but it did not dissolve. Catalysts generating light and free radicals. Part of the resin solution obtained was treated with a

accelerates. Since a reaction between the isocyanate "Cellosolve .." acetate solution of hexamethylenediamine in groups of esters and organic peroxide cata- such a ratio mixed that for each isocyanate lysers It is always probable that an amino group is preferably present in the copolymer was. The mixed solution turned into a solid gel within a few minutes.

The copolymer solution was also obtained by adding other amines, e.g. B. of ethylenediamine or 1,8-di-50 amino-p-menthan, gels quickly.

If, instead of the diamines, amino alcohols were used in such amounts that two reactive hydrogen atoms were present for every two isocyanate groups in the copolymer, soluble products were obtained which were obtained with 0.05% of its weight in azoisobutyronitrile 55 by baking at 100 ° to 200 ° in cross-linked, mixed in the heat and transferred in a dilatometer tube at 60 ° polymer curable films. The solutions are sated. The initial rate of polymerization
made 15% per hour im due to shrinkage

Application of a free radical forming catalyst, e.g. B. of azoisobutyronitrile (α, α'-bisazoisobutyronitrile), Methyl azo isobutyrate and the like

■ Example 1
/ J-isocyanate ethyl methacrylate,

CH ₂ = C (CH ₃ ) -COOCH ₂ CH ₂ NCO,

In contrast to a rate of 6.5 ° / ₀ for methyl methacrylate under the same conditions.

Example 2
10 parts / 3-isocyanate ethyl methacrylate and 90 parts

also gelled when left to stand for a few days at room temperature. These results were matched with the following Amino alcohols obtained: monoethanolamine, 60 diethanolamine, isopropanolamine, 3-aminobutanol, 7-amino-3,7-dimethyl-1-octanol and 4-amino-4-methyl-2-pentanol.

Simple glycols, e.g. B. hexamethylene glycol, diethylene glycol, 1,10-decanediol and 1,3-butylene glycol, however

Methyl methacrylate, polyols such as glycerol, pentaerythritol, sorbitol and azoisobutyronitrile were also mixed with 0.05 percent by weight. This mixture was heated under mannitol, reacted with the polymers and mixed under ^{reduced pressure at 80 ° C.} until it became syrupy. polymers of the isocyanate esters in practically the parts of the mixture were poured into flat glass molds, in the same way as the diamines discussed above, in which the crosslinked products, which were then tightly closed and curable in an oven for 24 hours, were heated to 60 °. After this heating it was 70 alkyd resins with free hydroxyl or carboxyl groups

react in a similar way and result in networked products example 5

A mixture of 20 parts of butyl acrylate, 5 parts of γ-isocyanate-S.T-dimethyl-1-octyl methacrylate, 1 part of one technical emulsifier, 75 parts of water, 0.017 part of ammonium persulfate and 0.009 part of sodium hydrosulfite was stirred at room temperature. As the polymerization proceeded, the temperature gradually rose at 45 °; then it dropped to room temperature. A dry rubbery film of the resulting Emulsion was soluble in toluene as long as it was not heated to 100 ° or higher. After that he got on Insoluble because of the crosslinking of the copolymer.

Claims (1)

Claim: Process for the production of polymers and copolymers, characterized in that monomeric isocyanate esters of the general formula Z —- COO —A-NCO, in which A is an alkylene group having 2 to 14 carbon atoms and Z is either CH ₂ = CH -, CH ₂ = C (CH ₃ ) -, CH ₂ = C (Cl) - or CH ₃ - CH = CH - means, alone or with another copolymerizable compound, the at least one group CH ₂ = C <contains, heated to the polymerization temperature in the presence of a reaction accelerator, preferably a catalyst which forms free radicals. © 709 849/438 1.58