DE1745350B2 - Block copolymer - Google Patents

Description

R ₁ NR,
in the Ri. R. · and Ri a hydrogen atom or

aliphatic hydrocarbon radicals with 1 to 6 carbon atoms mean and two of the hydrocarbon radicals can form a cyclic radical, and with Oxygen and subsequent block copolymerization with an acrylic compound of the general formula

R O R "

I Il /

CH ₂ = C-C-O-R 1 -N

R '"

10

in which R is a hydrogen atom or a methyl radical, R ' an alkylene radical with 1 to 8 carbon atoms and R "and R '" hydrogen atoms or alkyl radicals with I to 4 Carbon atoms mean in such an amount that in the block mixture polymer end product 0.1 up to 25% by weight, based on the weight of the end product of the block copolymer are.

The term »crystalline« used here stand! for the crystallinity * of a tempered polymer sample by X-ray analysis. The manufacture of Polypropylene and the types of ethylene / propylene copolymers mentioned are known. Usually these polymers are made from their monomers by polymerization with organometallic. complex, Catalysts often called »Zieglerw catalysts« are produced. These catalysts are obtained by reacting transition metal halides, in particular titanium halides, with metal hydrocarbon compounds, in particular aluminum trialkyls, Alkyl aluminum halides and alkyl aluminum hydrides. Random copolymers of propylene and ethylene are aged by polymerization of mixtures of F.-opylene and ethylene, while block copolymers by successive polymerization of propylene and Ethylene can be produced using the same catalyst. The details of each Polymerization processes are described in the literature and known to the person skilled in the art, which is why they are not here need to be listed further.

Extraction studies of the final block copolymer show that the acrylic compound according to the claims to the polypropylene / ethylene / polymer is bound, although the exact mechanism by which this occurs is not entirely known. It it is pointed out, however, that certain small amounts of homopolymer can be formed, which depends on the particular reaction conditions used; if these amounts are deemed undesirable viewed, they can be removed by extraction. The content of polymerized Acrylic compound can be used within the range of 0.1-25% by weight of the final block copolymer can be varied. The optimal concentration of the acrylic compound in the propylene polymer also varies the particular propylene polymer, the particular acrylic compound and the intended use of the block mixed polymer. Usually, the content of the polymerized acrylic compound is preferred between I to 15% by weight of the final block blend polymer product held. Suitable acrylic compounds used in the formation of the present invention new block blend polymers are used include

Dimethylaminoalkylmcihacrylai.

Dimethylaminoethyl acrylate,

15 MethylaminoStryliTiethacrylat,

Methylaminoethyl acrylate,

Aminoethyl acrylate,

Aminomethyl acrylate,

Diethylaminoethyl acrylate,

3- (dimethylamino) butyl acrylate,

4- (dimethylamino) butyl acrylate,

4- (dimethylamino) butyl methacrylate and

6- (Dimetl <ylamino) -2-ethylhexyl acrylate.
The block copolymerization process is described in detail in DE-OS 17 45 349, which was filed at the same time. Basically, the block copolymerization described there consists of a three-stage process in which - applicable to the new block copolymers according to the invention - in the first stage a mixture of the solid, propylene polymer free of unreacted olefin monomers and the described, organometallic, complex catalyst is formed; in the second stage, this mixture is treated with the nitrogen compound and with oxygen, which are then removed from the polymer mixture; and in the third stage the activated polymer mixture is brought into contact with the acrylic compound until the block copolymer is obtained. The polymer mixture formed in the first stage comes from the polymerization of propylene or of ethylene and propylene, which contain the organometallic, complex catalyst, before any deactivation of the catalyst has taken place. Any unreacted monomers, and preferably any solvent, are removed prior to activating the reaction to polymerize with the acrylic compound. The solid polymer / catalyst mixture is then treated with the nitrogen compound, preferably ammonia - although other nitrogen compounds falling under the general formula, such as gaseous, primary, secondary and tertiary amines, can be used - by adding an excess of ammonia at a pressure of 0.007 to 7 atm passes through the polymer / catalyst mixture. The NHi treated mixture is then flushed with an inert gas such as argon and a stream of oxygen is passed through the mixture which in turn is flushed with an inert gas. Although it is preferred to treat the mixture separately with the nitrogen compound and then with the oxygen, mixtures of NHj and O2 can also be used. The temperatures for carrying out the gas treatment are not critical and can be varied widely. Usually the temperature should not exceed the melting point of the polymer, so that the polymer is in a solid phase during the treatment with the activating gases. Suitable temperatures are therefore between 15 and 12 ° C. preferably between 15 and 66'C.

The third stage of the process used to form the new propylene block copolymers according to the invention is the addition of the acrylic compound to the treated, solid polymer reaction mixture. The film copolymerization takes place by adding the monomer in liquid form to the activated, solid polymer mixture. Owing to the exothermic polymerization, it is often unnecessary to heat the treated polymer for the purpose of block mixing polymerisation. Usually a reaction temperature of 15 to 121 "C" is used. preferably } 2 to 71 C ".

maintain. The liquid acrylic compound can be used in Can be used in bulk or in the form of a solution; a solution is used when using block copolymers with a low acrylic compound content. The use of solvents is also beneficial for suppressing any homopolymerization of the acrylic compound.

The degree of block copolymerization depends on the reaction conditions used and varies with the respective monomers. In general, however, a larger amount of the acrylic compound acts a higher degree of block interpolymerization; same good for a lower polymerization temperature. An excess of between 10 and 100% of that desired in the block copolymer is usually used Content of the acrylic compound used, preferably an excess between 20 and 40%. the Reaction times vary, but in general the reaction is allowed to come to an end, what is measured by temperature changes. Those used in combination with the acrylic compound, respectively Solvents are those that can break the acrylic bond but are otherwise inert in the system stay. Particularly suitable solvents: el are hydrocarbon solvents, such as hexane, cyclohexane, heptane, benzene and xylene.

The product obtained from the block copolymerization is then purified by not reacted acrylic compound removed and the catalyst residues according to customary cleaning processes for olefin polymers, which are obtained by polymerization with the described, organometallic catalysts were prepared, deactivated and precipitated. Such Processes can consist of washing the solid polymer product with water, dilute hydrochloric acid, Alcohol, or a combination thereof, or through the use of alcohol solutions, the chelating agents contain, in the manner described with the metallic components of the catalyst one Can form a chelate complex. Significant amounts of homopolymer are produced during block polymerization formed of the acrylic compound, these can be obtained by selective extraction of the slightly polar, organic solvents such as esters, ketones and ethers can be removed. The use of the solvent During the block copolymerization, the homogeneity of the block copolymers obtained can be reduced to enhance. A further homogenization of the block copolymers can also be achieved by you the polymer after its separation from the unreacted Mono.neren and after removal of the Mixing catalyst residues in the melt. Such melt blending is done in an extruder or any other device heretofore used for melt blending thermoplastic resins.

The block copolymers can continue, but this is no longer protected here. with unmodified propylene polymers are mixed, when the reduction in the content of acrylic compound in a particular copolymer it is asked for.

The block copolymers obtained are converted into films by customary processes for propylene polymers. Fibers and other objects. In articles produced in this way, the block copolymer according to the invention shows greater color absorption than the propylene polymers not modified in this way without significantly affecting the desirable mechanical properties of the unmodified propylene polymer. The block copolymers according to the invention are particularly receptive to acidic dyes.
Unless otherwise stated, all parts and percentages in the following examples are parts by weight and% by weight.

example 1

To a 1 liter heated steel reaction vessel was placed 0.65 grams Aluminum chloride / titanium chloride, AICb · 3 TiClj, and then 8.4 ml! molar diethyl aluminum monochloride given what an Al / Ti molar ratio of 2 corresponded. The reaction vessel was pressurized to 1.05 atmospheres with gaseous hydrogen, and 400 ml of liquid propylene monomer was added. The reaction mixture was heated from 24 to 60 ° C. with stirring and was kept on this for 40 minutes Temperature held. The reaction vessel was vented and depressurized to remove traces of propylene monomer 15 Mv.uten with gaseous Purged with argon. The system was sealed to the atmosphere, and the polypropylene Gaseous ammonia was added to the reaction vessel containing up to a pressure of 0.21 atü. To With stirring for 5 "minutes, the ammonia was deaerated and its traces by a stream of argon removed. The system was closed and oxygen was introduced into the reactor up to a pressure of

3n 0.7 atü initiated. After stirring for a further 5 minutes, the oxygen was vented and the reactor briefly with it Purged with argon gas.

Then 50 ml of distilled water were added to the reaction vessel. Given dimethylaminoethyl methacrylate at 35.5 ° C.

The temperature rose to 60.5 ° C. as a result of the exothermic reaction. where they sit without further heating for 40 minutes held. The reaction vessel was then cooled and opened. The reaction product was used 2 times equal parts of a hot isopropanol / rl'eptane mixture washed. The dried polypro-

pylene / poly-idimethylaminoäthylaerylatJ block copolymer weighed 230 g, had a density of 0.933 g / ml and a melt index (ASTM D-1238-62T) of 5.0 at 230 ° C. According to infrared analysis, the product contained 9% dimethylaminoethyl methacrylate. The extraction Part of the product with ethyl acetate showed no effect on the methyl acrylate content of the polymer. This shows the formation of a block copolymer.

A sample of the block copolymer was transformed from the melt into fibers with a diameter of 0.13 mm spun. A 2 g sample of the fiber was placed in a dilute acidic dye bath containing 0.5% Martius Yellow contained, immersed. After 10 minutes at about 50 ° C., the fiber was removed from the dye bath; and with one 1% solution of a commercial detergent. Then the yellow fiber was washed with water rinsed and dried. No color change was noted when a sample was dried

ho fiber 1 hour at 50 ⁰ C in a with carbon tetrachloride. The solution made from ligroin and amyl alcohol has been chemically purified.

The block copolymer was mixed with further polypropylene in order to reduce the poly (dimen-

b5 thylaminoethyl acrylate) to 3%. That The resulting polymer mixture showed excellent results after spinning into fibers from the melt Dye receptivity.

Comparative example

The polymerization procedure of Example I was repeated, but using the oxygen treatment step was omitted. The block copolymer obtained had a density of 0.909 g / ml and one Schmel / .indcx of 2.1 at 230 "C according to IR analysis The block mixed polymer contained 1.5% polymerized Dimethylaminoethyl methacrylate.

B e i s ρ i e I 2

(iemiil.) Example I a polypropylene was made. Then I want to give the resulting persimmon mixture I 2 μ Ethylene at a rate of 2 g / min added and the polymerization lasted 10 minutes continued. Then the cation mixture was deaerated and treated as in Example I with ammonia and oxygen. The activated Polvathslen <'PoKpiopylen Blockmischpolyinerisat was as in Example I mi Oi met hy I ·) mi noii ι hy I mc lhacry Κι ι mixed polymerized whereby a block polymerizate made of polypropylene / polyethylene / poly (el imei hy hi mi noii I hy I) methacrylate received.

Example j

Example I was using Mcthylami noäthylacrylat instead of Dimethylaminoäthylmcth acrylates repeated. So became a polypropylene / poly (mc thy la minoät hy lacry IaI) - block copolymers echo.

The above examples / own manufacture and leagues shadow of the crfindiingsgcmiilicn new block mixed po lyniensaie. Others can, of course according to the invention. iimino-substituted acrylic mono kidney according to the procedure given there, block mi sch polymerized sy ground.

Claims (4)

Patent claims: I. Block copolymer obtained by treating a crystalline polypropylene homopolymer or a crystalline random or block copolymer of propylene and ethylene, which is free of unreacted, monomeric olefin, but organometallic, complex catalysts contains, with a nitrogen compound of the general formula R ₁ -NR ₃ in which Ri, Rj and Rj represent a hydrogen atom or mean aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and two of the hydrocarbon radicals can form a cyclic radical, and with oxygen and subsequent block copolymerization with an acrylic compound of the general formula R O R " CH ₂ = C-C-O-R'-N R '" in which R is a hydrogen atom or a methyl radical, R 'is an alkylene radical having 1 to 8 carbon atoms and R "and R '" denote hydrogen atoms or alkyl radicals having 1 to 4 carbon atoms, in one such amount that in the block copolymer end product 0.1 to 25 wt .-%, based on the Weight of the block copolymer end product, are polymerized. 2. Block copolymer according to claim 1, characterized in that it has been obtained by treating first with the nitrogen compound and then with oxygen. 3. Block copolymer according to claim I and 2, characterized in that it is made using of dimethylaminoiithyl methacrylate. 4. Use of the block copolymers according to Claims I to J for the production of films and fibers. High molecular weight, crystalline polymers of propylene are used more and more in the form of films and fibers. Although they have many superior properties, one of their major disadvantages is the inability of these polymers to be dyed in fiber form and printed in film form. To overcome this problem, many methods have been proposed, such as / .. B. finishing of molded articles. Addition of compounds to increase the colorability of the finished Iasers obtained or addition of pigments to the polymer before it is shaped. However, all of these methods have disadvantages. So is z. B. the aftertreatment of films and fibers is not only costly, but also difficult to carry out on an industrial scale. The addition of compounds to the propylene polymer can cause exudation of the same during use of the fiber or film, thereby adversely affecting the hue and color of the material. The exuded material can furthermore be harmful to the material which comes into contact with the propylene polymer. Furthermore, the physical properties of the propylene polymer can be adversely affected by the addition of such compounds. The use of pigments that match the to polymer added before fiber production limits the choice of colors available essential, requires large mixing plants and a large starting mass of the polymer, does not allow Printing of the fabrics and films and often poses problems with regard to the color equality of different Approaches of the same, pigmented polymer. Although the copolymerization of propylene with Monomers capable of accepting dyes have been proposed for the purpose of imparting dyeability such interpolymerization often has an adverse effect on the reactivity of the Propylene in the polymer formation by having low polymerization rates and / or the formation a low molecular weight polymer causes. The direct copolymerization of monomers capable of dye uptake with propylene can also cause noticeable deterioration in desirable mechanical properties. JO In US-PS 30 49 508 the preparation of graft copolymers is described in which one first produces the corresponding olefin and z. B. deformed into fibers. These fibers are then ozonated and the activated polymer obtained in this way J5 subjected to graft polymerization. This procedure is awkward and expensive, since different reaction vessels are required for the various reaction stages. In particular, ozone treatment is also expensive, and not only. because the corresponding plants • to be laborious, but also take special precautionary measures because of the toxicity of ozone. There was still a need for a simple and inexpensive process for the production of block copolymers ^ The aim of the present invention is therefore to create new propylene polymers with improved Dyeability and printability. this modification in the dyeable propylene polymers none substantial damage to the desirable, mechanical Properties causes. Another aim is to create dyeable propylene polymers that Block copolymers of propylene and monomers which are dye-absorbent represent and where the monomers are physical properties 5ϊ of the Propylenpolymcrisatcs not adversely affect. The new block copolymers according to the invention, are obtained by treating a crystalline polypropylene homopolymer or a crystalline one random or block mixed polymers of propylene mi and ethylene, which is free from unreacted, monomeric Is olefin, but organometallic. Contains complex catalysts, with a nitrogen compound the general formula