DE1745350C3 - Block copolymer - Google Patents

Description

R ₁ -N - R.,
in which Ri, R2 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

CH ₂ = CCORN

R "

R '"

in which R is a hydrogen atom or a methyl radical, R ' an alkyl radical having 1 to 8 carbon atoms and R "and R '" are hydrogen atoms or alkyl radicals having 1 to 4 Carbon atoms mean in such an amount that in the block copolymer end product 0.1 to 23 wt .-%, based on the weight of the block copolymer end product, copolymerized are.

The term "crystalline" used here stands for the crystallinity of a tempered polymer sample by X-ray analysis. The production of polypropylene and the named types of ethylene / Propylene copolymers are known. These polymers are usually made from their monomers Polymerization with organometallic, complex catalysts, often referred to as "Zieglerw" catalysts manufactured. These catalysts are obtained by reacting transition metal halides, in particular titanium halides, with metal in hydrocarbon compounds, in particular aluminum trialkyls, Alkyl aluminum halides and alkyl aluminum hydrides. Random copolymers of propylene and ethylene are obtained by polymerization of mixtures of propylene and ethylene, r, 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 block copolymer end product show that the claims Acrylic compound is bound to the polypropylene / ethylene / polymer, although the exact mechanism after which this happens is not entirely known. It should be noted, however, that certain minor Amounts of homopolymer can be formed, depending on the particular reaction conditions used depends; if these amounts are considered undesirable, they can be removed by extraction removed. The content of the polymerized acrylic compound can be within the range of 0.1-25% by weight of the end product block copolymer can be varied. The optimal concentration of Acrylic compound in the propylene polymer varies with the particular propylene polymer, the particular one Acrylic compound and the intended use of the block copolymer. Usually the Content of polymerized acrylic compound preferably between 1 to 15% by weight of the end product of the block copolymer held. Suitable acrylic compounds used in forming the inventive new block copolymers are used, t >> include

Dimethylaminoethyl methacrylate,

Dimethylaminoethyl acrylate,

Methylaminoethyl methacrylate,

Methylaminoethyl acrylate,

Aminoethyl acrylate,

Aminomethyl acrylate,

Diethylaminoethyl acrylate,

3- (dimethylamino) butyl acrylate,

4- (dimethylamino) butyl acrylate,

4- (dimethylamino) butyl methacrylate and

6- (Dimethylamino) -2-ethylhexyl acrylic
The process of block copolymerization 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, of unreacted olefin monomer free propylene polymer 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 NHj-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 the solid phase during the treatment with the activating gases. Therefore, suitable temperatures are between 15 and 121 ° C, preferably 15-66 ⁰ C.

The third stage of the used to form the novel propylene block mixed polymers according to the invention The method consists in adding the acrylic compound to the treated solid polymer reaction mixture. The block copolymerization is carried out by adding the monomer in liquid form to the activated, solid polymer mixture. Because of the thermal polymerisation it is often unnecessary to do this to heat treated polymer for the purpose of block copolymerization. Usually becomes a reaction temperature from 15 to 121 ° C, preferably 32 to 71 "C.

upright 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: the same applies to 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 each case in combination with the acrylic compound Solvents are those that can dissolve the acrylic compound but are otherwise inert in the system stay. Particularly suitable solvents are hydrocarbon solvents, like 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 after the usual cleaning process, for jo Olefin polymers produced by polymerization with the organometallic catalysts described have been deactivated and fails. Such procedures may consist of washing the solid Polymer product with water, dilute hydrochloric acid j-j re. 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. There are noticeable amounts of homopolymer during block copolymerization of the acrylic compound, these can be extracted by selective extraction with slightly polar, organic solvents such as esters, ketones and ethers can be removed. The use of the solution 4i 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 the polymer after its separation from the unreacted monomers and after removal of the Catalyst residues in the melt mix. 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 special mixed polymer sat is desired.

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 invention shows ße Blockmischpoiymcrisiti a greater color absorption capacity than the propylene polymers not modified in this way without significantly affecting the desirable mechanical properties of the unmodified propylene polymer. The invention Block copolymers 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 heated 1-liter steel reaction vessel was placed 0.65 g Aluminum chloride / titanium chloride, AICI3 · 3 TiCIj, and then 8.4ml! molar diethylaluminum monochloride given, which corresponds to a molar ratio of Al / Ti 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 stirred with Heated to 60 ° C for 24 and kept at this temperature for 40 minutes. The reaction vessel became vented or relaxed and to remove traces of propylene monomer 15 minutes 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 0.7 alü 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 des'. Dimethylaminoälhylmethacrylat given at 35.5 ° C. As a result of the exothermic reaction, the temperature rose to 60.5 ° C., where it could stand for 40 minutes without further heating held. Then the reaction vessel was cooled and opened. The reaction product was used 2 times equal parts of a hot isopropanol / heptane mixture washed. The dried polypro-

pylene / poly-dimethylaminoethyl acrylate / 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 acetal 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 spun from the melt into fibers 0.13 mm in diameter. A 2 g sample of the fiber was immersed in a dilute acidic dye bath containing 0.5% Martius Yellow. After 10 minutes at about 50 ° C., the fiber was removed from the dye bath and washed with a 1% strength solution of a commercially available detergent. Then the yellow fiber was rinsed with water and dried. No change in color was found when a sample of the dried fiber was ^{chemically cleaned for 1 hour at 50 °} C. in a solution prepared with carbon tetrachloride, ligroin and amyl alcohol.

The block copolymer was mixed with further polypropylene in order to reduce the content of poly (dimethylaminoethyl acrylate) to decrease to 3%. The polymer mixture obtained showed excellent results after spinning into fibers from the melt Dye uptake ability.

Comparative example

The polymerization procedure of Example I was repeated except that the oxygen treatment step was omitted. The Blockmischpo- "> lymerisat obtained had a density of 0.909 g / ml and a Schmelzindcx of 2.1 at 230 ° C. According to IR analysis of the block copolymer contained 1.5% polymerisicrtes Dimcthy liiminoathylmcthacryli.it.

K)

Example 2

According to Example 1, a polypropylene was produced. Then, 12 g were added to the reaction mixture obtained Ethylene was added at a rate of 2 g / min and the polymerization continued for a further 10 minutes continued. Then the reaction mixture was deaerated and as in Example I with ammonia and oxygen treated. The activated polyethylene / polypropylene block polymer was copolymerized as in Example 1 with dimethylaminoethyl methacrylate, whereby a block copolymer of polypropylene / polyethylene / poly (dimethylaminoä thy I) - met h acrylate received.

Example 3

Example 1 was made using methylaminoethyl acrylate instead of dimethylaminoethyl methacrylate repeated. A polypropylene / poly (methylaminoethyl acrylate) block copolymer was made obtain.

The above examples show the production and properties of the new block copolymers according to the invention. Of course, other amino-substituted acrylic monomers according to the invention can also be used are block copolymerized by the processes specified there.

Claims (4)

Patent claims: 1. Block copolymer obtained by treating a crystalline polypropylene homopolymer or a crystalline random or block copolymer of propylene and ethylene, the 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, R2 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, = 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 mixed polymer according to claim 1, characterized in that it has been obtained by treating first with the nitrogen compound and then with oxygen. 3. Block mixed polymer according to claim 1 and 2, characterized in that it is made using of dimethylaminoethyl methacrylate has been produced. 4. Use of the block copolymers according to Claims 1 to 3 for the production of films and fibers. High molecular weight, crystalline polymers of propylene continues to find use in the form of films and fibers. Although they are superior to many Have properties, one of their main disadvantages is the inability of these polymers to in Fiber form to be dyed and printed in film form. To overcome this problem are many Methods have been proposed such as. B. Post-treatments of molded objects, addition of Compounds for increasing the dyeability of the finished fiber obtained or adding pigments to the polymer before it is deformed. However, all of these methods have significant disadvantages. So is z. B. the aftertreatment of films and fibers not only costly, but on an industrial scale also difficult to perform. The addition of compounds to the propylene polymer can be They cause exudation during fiber or film use, creating tint and color of the material are affected. The exuded material can still be harmful to the Material that comes into contact with the propylene polymer. Furthermore, the physical Properties of the propylene polymer adversely affected by the addition of such compounds will. The use of pigments, which are added to the polymer before fiber production, limits the choice of available. Colors essential, requires large mixing plants and ones large initial mass of the polymer, does not allow printing on the fabrics and films and often poses problems regarding the color equality of different batches of the same, pigmented polymer. Although the interpolymerization of propylene with monomers that can absorb dyes for the purpose It has been proposed to impart dyeability, such interpolymerization often has unfavorable effect on the reactivity of the propylene in the polymer formation by being low Polymerization rates and / or the formation of a low molecular weight polymer causes. The direct interpolymerization of monomers capable of dye uptake with propylene can also cause noticeable deterioration in desirable mechanical properties. 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 3- "i subjected to graft polymerization. This process is awkward and expensive, since different reaction vessels are required for the different reaction runs. In particular, the ozone treatment is expensive, and not only because of the corresponding systems are expensive, but also because special precautionary measures are necessary because of the toxicity of ozone are. There was thus still a need for a simple and inexpensive method of manufacture of block copolymers !!. ■)> The aim of the present invention is therefore Creation of new propylene polymers with improved colorability and printability, this modification in the dyeable propylene polymers no significant damage to the desirable mechanical ") 0 causes frilly properties. Another goal is that Creation of dyeable propylene polymers, the block copolymers of propylene and monomers, which are dye-receptive, and where the monomers represent the physical properties Do not adversely affect T> of the propylene polymer. The inventive block copolymers, are obtained by treating a crystalline polypropylene homopolymer or a crystalline one random or block copolymer of propylene bo and ethylene, which is free from unreacted, monomeric Is olefin. but contains organometallic, complex catalysts, with a nitrogen compound the general formula R,