DE1745350A1 - Block copolymer - Google Patents

Description

PAT E N TA N WA LT E

dr. w. Schalk · dipl-inc. peter Wirth ***> ^ 3U

DIPL.-ING.G. E. M. DANNENBERG · DR. V. SCHMIED-KOWARZIK

6 FRANKFURTAM MAIN

GR. ESCHENHEIMER STR. 39 '-! F /' nTC

SC-25

Hexall LRU ₁ J and Chemical Company o4öO Beverly Boulevard On ^ alea, Ga. / USA

Bloolon copolymer

The present invention also relates to new ßlooianiochpoly- M nierisate from propylene, in particular to new olocic copolymers from propylene polymers]! and functionally substituted acrylic monomers.

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 drawbacks is the inability of these polymers to be colored in fiber and printed in film form. To overcome this problem, many have been Verfanren vorgescnXagen Λ, such as post-treatments is molded articles, addition of compounds to enhance the dyeability of the obtained finished fiber or the addition of pigments to the polymer prior to its deformation. However, all of these methods have local disadvantages. For example, the aftertreatment of films and fibers is not only costly, but also difficult to carry out on an industrial scale. The addition of compounds

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to the propylene polymer, exudation of the same can occur during

Tint the fiber or film use effect, making JHttnt and color The sweaty material can still be harmful to the material that 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 are added before the fiber division, limits the choice of available colors significantly, requires large mixing systems and a large starting mass of the polymer, does not allow printing on the fabrics and films and often poses problems with regard to the color equality of different batches of the same, pigmented polymer. Although the interpolymerization of propylene with monomers that can take up dyes has been proposed for the purpose of imparting a dyeability, such interpolymerization often has an adverse effect on the reactivity of the propylene in polymer formation, in that it low rates of polymerization and / or the formation of a low molecular weight Polymer causes. The direct interpolymerization of monomers capable of dye uptake with the propylene can furthermore cause noticeable destruction of the desirable mechanical properties · ^f

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The aim of the present invention is therefore to create new propylene polymers with improved colorability and printability, this modification in the dyeable propylene

Damage polymers no essential 3eggοtenne of the desirable, Mechanical properties brought about Another goal is the creation of dyeable propylene polymers, the block copolymers of propylene and monomers that do not absorb dyes are, represent and where the monomers do not adversely affect the physical properties of the propylene polymer

The novel polymers according to the invention are block copolymers polymerize from a propylene polymer and one, amino-substituted acrylic .. ionomers of the general formula

BO E "

in which E stands for hydrogen or a methyl group, E * stands for an alkylene radical with 1-8 carbon atoms and R "and R" ¹ mean hydrogen or an alkyl radical with 1- * 4 carbon atoms «

The new propylene polymers are obtained by means of copolymers! " cation of the amino-substituted acrylic monomer of the above Formula with a preformed polymer of propylene. Those involved in the formation of the new block copolymers according to the invention Propylene polymers used are crystalline homopolymers of propylene and crystalline, random or block mixed poly-

Propylene and
merisate of / ethylene. The term "crystalline" used here

stands for the crystallinity of an annealed

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Polymer sample by X-ray analysis. The production of poly

of the mentioned
Propylene and types of ethylene / propylene copolymers are known. These polymers are usually prepared from their monomers by polymerization with organometallic, complex ^{catalysts, often referred to as "Ziegler-M} catalysts. These catalysts are obtained by reacting transition metal halides, in particular titanium halides, with metal hydrocarbyl compounds, in particular aluminum trialkyls, alkyl aluminum halides and alkyl aluminum hydrides. Random mixed polymers Propylene and ethylene are obtained by polymerizing mixtures of propylene and ethylene, while block copolymers are produced by successive polymerization of propylene and ethylene using the same catalyst.The details of the respective polymerization processes are described in the literature and are known to the person skilled in the art, which is why they are not here need to be listed further

That for the formation of the block copolymers according to the invention aminosubstituted, aorylieohe monomers used is then in one suitable for the formation of a block copolymer Way polymerized in the presence of the propylene polymer Extraction studies of the bloc copolymer show that the polymerized, amino-substituted aorylieohe comonomers is bound to the hydrocarbon polymer, although the The exact mechanism by 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; if

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these amounts are considered undesirable, they can through Extraction to be removed. The content of polymerized, aminoau Substituted, acrylic comonomer can be used within the range varies from 0.1-25% by weight of the block copolymer will. The optimal concentration of the aminosub titled, acrylic comonomers in the propylene polymer varies with the particular propylene polymer, the particular, amino-substituted, acrylic comonomers and the intended use of the block copolymer. Usually the content will be

preferably polymerized, amino-substituted comonomer / between 1-15 % By weight of the block copolymer held ". Suitable, polar Coinonomers that are used in the formation of the new block copolymers according to the invention used include dimethylaminoethyl methacrylate, diiaethylaminoethyl acrylate, methylaminoethyl methacrylate, Methylaminoethyl acrylate, aminoethyl acrylate, aminomethyl acrylate, Diethylaminoethyl acrylate, 3- (dimethylamine) butyl acrylate, 4- (Dimethylamine) butyl acrylate, 4- (DJ.methylamino) butyl methaorylate, 4 - (! Ethylamino) acrylate, 4- (methylamino) methacrylate and 6- (dimethylamino) -2-ethylhexyl acrylate,

The preferred process for the preparation of the block copolymers according to the invention consists of the following one Polymerizing the olefin, e.g. propylene or propylene and ethylene, and then the amino-substituted acrylic monomer, Although some bloomia polymerization is achieved when the amino-substituted, aorylic monomers dom propylene polymer after its formation and before the deactivation of the organometallic catalyst is added directly, there is a change of the polymerization environment preferred, thereby increasing the ability

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for interpolymerization of the amino-substituted acrylic monomer is significantly improved with the propylene polymer. The procedure for changing the polymerisation environment is described in detail in the "*" submitted at the same time In principle, there is the blookmachpolymerization described there in a three-stage process in which - applicable to the novel block copolymers according to the invention - in the first stage a mixture of the solid, unreacted olefin monomer free propylene polymers and the organometallic complex catalyst described is formed; in the In the second stage, this mixture is treated with a nitrogen compound and with oxygen, which is then mixed with the polymer be removed; and in the third stage the activated polymer mixture with the amino-substituted, aorylic Monomers brought into contact until you get daa block copolymer receives. The polymer mixture formed in the first stage preferably originates from the polymerization of propylene or of ethylene and propylene, which form the organo-metallic complex Contain catalyst before any deactivation of the catalyst has occurred. All unreacted monomers and preferably Any solvents are also removed before the Removed polymerization reaction with acrylic monomer. The solid polymer / catalyst mixture is then with a St idet off connection, preferably Anauoiiialc - although also other Stickst of! 'compounds, such as gaseous, px * i: ^ taO, secondary and tertiary amines, can be used - treated by an ammonia control is carried out at a pressure of 0.007-7 atm

⁺ Registration, internal number GO-27 »3er.No. 600 039 dated December 8, 1966 in the USA ("Process for Slookmiaohpolymerisation") ·

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through the polymorisate / catalyst assembly. Then the ammonia-treated mixture is purged with an inert gas, such as argon, and an oxygenate . gets through the mix

then
passed, which / in turn v / ird flushed with an inert gas.

Although it is preferred to separate the mixture with the nitrogen compound; and then r "it . To treat oxygen, mixtures of NH_ and O ₂ 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 after treatment with the activating gases. Therefore, suitable temperatures are between 15 to 121 ⁰ C, preferably between 15-66 ⁰ C.

The third stage of the preferred process used to form the novel propyl coolant copolymers is the addition of the amino-substituted acrylic constituents to the treated, solid polymer reaction mixture. The block copolymerization takes place by adding the monomer in liquid form to the activated, solid polymer mixture. etc. Due to the exothermic polymerization, it is often unnecessary, the treated polymer block copolymerization in order to heat "Usually, a Reaktiorjeteaperatur of 15-121 ⁰ C, preferably 32-71 ⁰ C, maintaining s · The liquid comonomers can be used in bulk or in the form of a Solution are used ι a solution is used when bloctanie polymerizate with a low content; to aaiinosubstituierte.il, acrylisehern monomers. The use of solvents is also advantageous in suppressing any homopolymerization of the amino substituted aorylic monomer.

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The degree of bloc copolymerization depends on the reaction conditions used and varies with the particular monomer. In general, however, a larger amount of the amino-substituted acrylic comonomer causes a higher degree of blookmisohpolymerization; the same applies to a lower polymer ion temperature. Usually, an upper weft between 10-100 fo of the desired Blookmischpolymerisat content is used of the polar comonomers, preferably an excess of 20-40 #. The reaction times vary, but in general the reaction is allowed to come to an end, which is measured by temperature changes. The solvents used in each case in combination with the polar comonomer are those which can dissolve the polar comonomer, but otherwise remain inert in the system suitable solvents are hydrocarbon solvents such as hexane, cyolohexane, heptane, benzene, xylene and the like.

Obgltieh it for the production of the block copolymers according to the invention preferred is only the amino-substituted acrylic To use monomers, the present invention also includes those block copolymers which result from the polymerization of mixtures of the amino-substituted acrylic monomers with other polar comonomers, especially alkyl esters of Acrylic and methacrylic acids, acrylic and methacrylic acid, acrylonitrile and styrene, with the activated propylene polymer come

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The product obtained from the block copolymerization is then purified by removing unreacted polar comonomer and deactivating and precipitating the catalyst residues by conventional purification processes for olefin polymers produced by polymerization with the organometallic catalysts described. Such methods can consist in washing the solid polymer product with waaser, dilute hydrochloric acid, alcohol or a combination thereof or by using alcohol solutions which contain gelatinizing agents which can chelate in the manner described with the metallic components of the catalyst. If noticeable amounts of homopolymer of the polar comonomer are formed during the block copolymerization, these can be removed by selective extraction with slightly polar, organic solvents such as esters, ketones and ethers. The use of the solvent during the block copolymerization can improve the homogeneity of the block copolymers obtained. Further homogenization of the block copolymers can also be achieved by mixing the polymer in the melt after it has been separated off from the unreacted monomers and after the catalyst residues have been removed. Such solute blending takes place in an extruder or any other device heretofore used for melt blending thermoplastic resins.

The block copolymers can be further mixed with unmodified propylene polymers if it is desired to reduce the content of amino-substituted, aorylic comonomers in a particular copolymer.

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The block copolymers obtained are converted into films, fibers and others by customary processes for propylene polymers Objects shaped. In articles produced in this way, the bloom isoh polymer according to the invention shows a larger one Ink receptivity 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

The present invention has been described above with particular reference to the modification of propylene polymers. Of course, the same processes can also be used for the production of block monopolymers from other ole fi n polymers in a mixture with the organometallic isohen, complex catalysts and the amino-substituted aorylisohen Monomers.

The following examples illustrate the present invention without limiting it. Unless otherwise specified, are all parts and percentages are parts by weight and #.

Example I _-

In a heated 1-1 steel reaction vessel, 0.65 g of aluminum chloride / titanium chloride, AlCl ₅ .JTiCl ^, and then 8.4 ecm 1 molar diethylaluminum monoxide, which corresponded to an Al / Ti molar ratio of 2, were placed. The reaction vessel was brought to a pressure of 1.03 atmospheres with gaseous hydrogen, and 400 OD'm of liquid propylene monomer were added. the

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Reaction mixture was heated with stirring from 24 ° to 6O ⁰ C. and 40 minutes · maintained at this temperature The Eeaktionsgefäß, was vented or flushed · relaxed and to remove traces of propylene monomeric * 15 minutes by argon gas. The system was sealed to the atmosphere, and gaseous ammonia was added to the reaction vessel containing polypropylene to a pressure of 0.21 atm. After stirring for 5 minutes, the ammonia was vented and traces of the legs were removed by a stream of argon. The system was sealed and oxygen was introduced into the reactor to a pressure of 0.7 atm. After stirring for a further 5 minutes, the oxygen was vented and the reactor was briefly flushed through with argon gas.

Then 50 ecm of distilled water were placed in the reaction vessel. Dimethylamineäthylmethaorylat at 35 _t 5 ⁰ C. given. By the exothermic reaction, the temperature rose to 60.5 ⁰ C, where it remained without further heating 40 minutes. The reaction vessel was then cooled and opened. The reaction product was washed twice with equal parts of a hot isopropanol / heptane mixture. The resulting dried polypropylene / poly (dimethylaminoethyl aorylate) -BlDokmisohpolymeriBat weighed 230 g, had a density of 0.933 g / oom and a melt index (ASTM D-1238 -621) of 5.0 at 23O ⁰ C. According to infrared analysis, the product contained 9 # Dimethylaminoäthylmethaorylat. Extraction of part of the product with ethyl alcohol showed no effect on the methyl aylate content of the polymer. This shows the formation of a block copolymer «·

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A sample of the block copolymer was spun from the melt into monofilaments 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 ⁰ C., the fiber from the dye bath was removed and washed with a solution of 1- $ Onea commercial detergent. Then the yellow fiber was rinsed with water and dried. It was found no change in color when a sample of the dried fiber 1 hour at 5O ⁰ C. in a with carbon tetrachloride,

and the solution made from amyl alcohol has been chemically purified.

The Blockmisohpolymerisat was mixture ^ to the content of poly (dimethylaminoäthylaorylat) to decrease with further polypropylene 3 1 ". The polymer obtained, after being pinned to form fibers from the melt, exhibited excellent dye absorption capacity.

Example 2

The polymerization procedure of Example 1 was repeated, except that the acidity of the treatment stage was omitted. The block copolymer had a density of 0.909 g / cc and a melt index of 2.1 at 230 ⁰ C. According to IR analysis contained the Blockrnischpolymerisat 1.5 $> polymerisiertea Dime thy laruinoäthylwethacrylat.
B is ρ i el 3

According to Example 1, a polypropylene was produced. Then, to the obtained reaction mixture, 12 g of ethylene was added at one rate of 2 g / min was added and the polymerization continued for a further 10 minutes. The reaction mixture was then vented

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and treated as in Example 1 with ammonia and oxygen. That activated polyethylene / polypropylene block copolymer was copolymerized with dimethylaminoethyl methacrylate as in Example 1, whereby a Blookmischpolymeriaat made of polypropylene / polyethylene / poly (dimethylaminoethyl) methaorylat received

Example £

Example 1 was made using methylaminoethyl aorylate instead of dimethylaminoäthylmethaorylates repeated · So was a polypropylene / poly (methylaminoethyl acrylate) block copolymer received sat.

The above examples show the manufacture and properties of the new block copolymers according to the invention. Of course can also use other amino-substituted aorylic ones according to the invention Monomers are block polymerized by the processes specified there.

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Claims (6)

Claim 1. Block copolymer consisting of a crystalline propylene polymer and 0.1 to 25 wt .- ^ ₁ based on the weight of the block copolymer, of an amino-substituted acrylic comonomer of the formula ^R ° R " OH ₉ -CCOR '-N in which R represents hydrogen or a methyl group, R ^{1 represents} an alkylene radical with 1 to θ carbon atoms and R ″ and R ″ ^{1 represent} hydrogen or alkyl radicals with 1 to 4 carbon atoms · 2. Block copolymer according to claim 1, characterized in that the propylene polymer is polypropylene. 3 * Blockmieohpolymerisat according to claim 1, characterized in that the radical R ^{1 of} the amino-substituted acrylic monomer is an ethylene radical. 4. Block copolymer according to Claim 1, characterized in that the radicals R "and R ¹ " of the amino-substituted acrylic monomer are methyl radicals. 5. Block copolymer according to claim 1, characterized in that the radical R ^{1 of} the amino-substituted aoryl monomer is an ethylene radical and the radicals R "and R" ^{1 are} methyl radicals. - 14 - 209813/1666 5. block copolymer according to claim 1, characterized in that daaa the amino-substituted acrylic monomer is dimethylaminoethyl methacrylate. 6. block copolymer according to claim 1 to 5 t, characterized in that that it is made into a fiber. 7 · Block mixed polymerisation according to claims 1 to 5 »characterized in that that it has been made into a film. ™ The patent attorney ι 209813/1666