FI92071C - Method for (mixed) modification of polymers using organic peroxides - Google Patents

Description

92071

A process for (mixed) modifying polymers using organic peroxides

The invention relates to a process for the modification of (mixed) polymers using organic peroxides and to molded articles containing these modified (mixed) polymers.

It is well known that the incorporation of epoxide groups or other functional groups into suitable (se-10 ka) polymers can lead to improved (mixed) physical and chemical properties of the polymers. Public-World Rubber World 191 (6) p. 15 - 20 (1985) and Rubber Developments, Vol 38 No. 2, p. 48-50 (1985), for example, the incorporation of epoxy groups into natural rubber provides advantageous properties such as increased glass transition temperature, increased oil resistance, reduced gas permeability, improved resilience, increased tensile strength and improved adhesion to other materials such as silicon. other polymers, more particularly PVC, which is necessary in the manufacture of polymer blends. In addition, it is possible for these modified polymers to be subjected to chemical reactions typical of epoxy groups. Examples include i) crosslinking of the polymer with polyfunctional compounds having active hydrogen atoms, such as polyamines and diemaxic acids, which reaction is described in Chemical Reactions of Polymers, E.M. Fettes (Eds.), Interscience Publications, New York (1964), Chapter II, Part E, 30, p. 152, ii) covalent attachment of antioxidants containing amino groups in the molecule to a polymer, the reaction of which is described in Journal of Polymer Science, Polymer Letters Edition, Vol. 22, 327-334 (1984), and iii) reaction with fluorine-containing compounds such as trifluoroacetic acid to give a polymer, 292071, with improved lubricity and ozone resistance, which reaction is described in WO 85/03477.

In general, epoxide groups are attached to (mixed) polymers by so-called epoxidation reactions, in which an unsaturated (mixed) polymer in the form of a latex or dissolved in an organic solvent is reacted with an epoxide reagent suitable for a saturated aldehyde oxide. However, the TMIIS methodSHS has 10 several disadvantages. Above all, the requirement that the (mixed) polymer should be unsaturated means that only a very limited (mixed) polymer group can be associated with epoxide groups. For example, the whole group of saturated (mixed) polymers is included outside the functionalizers. Second, the use of solvents results in a purification step following the epoxidation reaction. In addition to the disadvantages associated with the production process of such a step, the use of solvents has obvious disadvantages in terms of energy consumption and environmental pollution. Third, the epoxidation reaction always involves side reactions, such as the formation of hydroxyl groups, acyloxy groups, ether groups, keto groups, and aldehyde groups, which weakens the proposed incorporation of epoxide groups.

Finally, it is worth mentioning that there is a known • ·. 25 epoxy groups contain (mixed) polymers by copolymerization and graft polymerization of monomers containing a glycidyl group (see Journal of Polymer Science, Vol. 61, pp. 185-194 (1962), Makromol. Chem., Rapid Commun. 7, pp. 143-148 (1986) and Die Angewandte 30 Macromolecular Chemistry 48, pp. 135-143 (1975)). However, inevitably, the formation of undesired by-products, such as the formation of homopolymers of a monomer containing a glycidyl group, is considered to be a disadvantage in the actual application. In addition, only a limited number of modified (mixed) polymers can be prepared by these methods.

The object of the present invention is to eliminate the above-mentioned disadvantages in well-known methods for attaching epoxide groups to (mixed) polymers, and. to that end, it provides a process in which certain organic peroxides are used to modify (mixed) polymers. The invention relates to a process for modifying (mixed) polymers using an organic peroxide, in which process the peroxide is brought into contact with the (mixed) polymer and the peroxide is decomposed. The invention is characterized in that the peroxide is an organic peroxide of the general formula H r2 r3

III I

R - 0 - 0 - C - C = C

1.1 R1 R4 Jn wherein n is 1 or 2; R 1 is hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms; R 2, R 3 and R 4 may be the same or different and are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms; R 1 and R 2, R 1 and R 3, R 1 and R 4, R 2 and R 3, R 2 and R 4 or R 3 and R 4 together form an alkylene group having 3 to 12 carbon atoms: "* 25 when n - 1, R * t -alkyl group which is not or is substituted by a hydroxyl group and containing 4 to 18, preferably 4 to 12, carbon atoms, a t-alkenyl group having 5 to 18, preferably 5 to 12 carbon atoms, or a group of the general formula CH3 chr ch3 ^ 4 92071 when η - 2, R = an alkylene group having 8 to 12 carbon atoms, both of which have a tertiary structure, or an alkynylene group of 8 to 12 carbon atoms, each of which has a tertiary structure.

Alkyl groups, alkenyl groups and alkylene groups may be linear or branched unless otherwise indicated.

It is further attributed to the fact that t-butylallyl peroxide is known from Bull. Soc. Chim. France No. 10 2, 198-202 (1985) and tMmM peroxide is mentioned in tåssM because it is capable of 2,3-epoxypropanation of organic solvents with labile hydrogen atoms. As the solvent, cyclohexane, tetrahydrofuran, propionic acid, propionic anhydride, methyl propionate, acetonitrile and trichloromethane are mentioned. The article also mentions the need for an auxiliary initiator with a lower degradation state than with t-butylallyl peroxide. Nevertheless, the Tarna article does not disclose this invention.

Compounds of general formula R 1 - O - 0 - R 2 in which R 1 is a tertiary organic radical, R 2 is an unsaturated aliphatic or cyclic aliphatic radical, in particular allyl t-butyl peroxide, allyl t-amyl peroxide. sidi, allyl-e, α-dimethylbenzyl peroxide and meta-allyl-t-butyl peroxide, are known per se from U.S. Pat. No. 2,516,649. to polymerize the compounds.

peroxides

The peroxides according to the invention are of the formula (I) shown above and belong to the class of dialkyl peroxides. They can be prepared in a conventional manner. In the preparation of dialkyl peroxides, pri-. · 5 92071 of an earth or secondary alkenyl derivative of the general formula H R2 r3

I I I

5 x - C - C * C (II) R 1 R 4 wherein R 1 - R 4 are as defined above and x is Cl, Br, OSO 2 CH 3, 0,0,0-CH 3 or a different leaving group.

Examples of suitable starting compounds are allyl bromide (2-propenyl bromide), 2-methyl-2-15 propenyl bromide (methylallyl bromide), 1-methyl-2-propenyl bromide, 1-ethyl-2-propenyl bromide, 1-propyl-1-2-propenyl bromide, 1-isopropyl-2-propenyl bromide, 2-t-butyl-2-propenyl bromide, 2-neopentyl-2-propenyl bromide, 2-butenyl bromide, 1-methyl-2-butenyl bromide, 3-methyl-2-butenyl bromide, 2 , 3-dimethyl-2-butenyl bromide, 1,2,3-trimethyl-2-butenyl bromide, 2-cyclohexenyl bromide.

Preferably, allyl bromide is utilized due to its easy availability. In the preparation of these dialkyl peroxides, the primary or secondary alkenyl halide II can be reacted with the hydroperoxide in the usual manner in an alkaline support in the presence of a phase transfer catalyst.

Examples of suitable hydroperoxides include: 1,1-dimethyl-2-propenyl hydroperoxide, 1-methyl-1-ethyl-2-propenyl hydroperoxide, 1,1-diethyl-2-propenyl hydroperoxide, 1-methyl-1-isopropyl-2 -propenyl hydroperoxide, 1,1-diisopropyl-2-propenyl hydroperoxide, t-butyl hydroperoxide, 1,1-dimethylbutyl-35 hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 6,92071 1,1-dimethyl- 3-hydroxybutylhydroperoxide, t-pentylhydroperoxide, 1-ethenyl-1-hydroperoxycyclohexane, 1- (1-hydroperoxy-1-methylethyl) -4- (1-hydroxy-1-methylethyl) benzene, 1- (1-hydroperoxy- 1-methylethyl) -4-methyl-5-cyclohexane, 1- (1-hydroperoxy-1-methylethyl) benzene (α-cumyl hydroperoxide), 1,3-di (1-hydroperoxy-1-methyl-1- phenyl) ethane, 1,4-di (1-hydroperoxymethyl-1-phenyl) ethane, 1,3,5-tri (1-hydroperoxy-1-methyl-phenyl) ethane, 2,5- dimethyl-2,5-dihydroperoxy-10-hexane, 2,5-dimethyl-2,5-dihydroperoxy-3-hexine.

Typical examples of dialkyl peroxides which can be used according to the invention are 3-allylperoxy-3,3-dimethylpropene, 3- (1-methyl-2-propenylperoxy) -3,3-dimethylpropene, 2-allylper-15-oxy-2 -methylpropane, 2- (1-methylmethyl-2-propenylperoxy) -2-methylpropane, 1-allylperoxy-1,1-dimethylbutane, 1-allylperoxy-1,1,3,3-tetramethylbutane, 1-allylperoxy-1,1 -dimethyl-3-hydroxybutane, 1-allylperoxy-1,1-dimethylpropane, 1- (1-methyl-2-propenylperoxy) -20 1,1-dimethylpropane, 1- (1-allylperoxy-1-methylethyl) - 4-methylcyclohexane, (1- (2-methyl-2-propenylperoxy) -1-methyl-1-phenyl) ethane, (1-allylperoxy-1-methyl-1-phenyl) ethane, (1- ( 1-methyl-2-propenylperoxy) -1-methyl-1-phenyl) ethane, 1,3-di (1-allylperoxy-1- [α] 25 methyl-1-phenyl) ethane, 1,4-di ( 1-allylperoxy-1-methyl-1-phenyl) ethane, 1,3,5-tri (1-allylperoxy-1-methyl-1-phenyl) ethane, 2,5-di (allylperoxy) -2.5 -dimethylhexane, 2,5-di (allyl peroxy) -2,5-dimethyl-3-hexine, (1- (2-cyclohexenylperoxy-1-methyl-1-phenyl) ethane.

Peroxides can be prepared, transported, stored and used as such or in the form of powders, granules, solutions, aqueous suspensions or emulsions, pastes, etc.

Which of these forms is preferred depends in part on how easy it is to introduce peroxide into the closed systems. Safety points (light sensitivity-> · 7 92071 reduction) may also be relevant. Examples of suitable photosensitizers are solid supports such as silica, lime. and alumina, inert plasticizers or solvents such as mono- or dichlorobenzene and water.

(Modification of mixed polymers

These peroxides are ideally suited for use in the preparation of (mixed) polymers containing epoxy groups, in which process the unmodified (mixed) polymer is contacted with the peroxide, whereby the peroxide decomposes completely or almost completely. The peroxide can be contacted with the (mixed) polymer in various ways depending on the subject of the modification. For example, if the epoxide groups are to be present on the surface of the (mixed) polymeric target, the peroxide may be used on the surface of the material to be modified. It is often desirable for the epoxide groups to be homogeneously distributed in the (mixed) polymer matrix. In that case, the peroxide may be mixed with the material to be modified, which may be either in the molten state, in solution or, in the case of the elastomer, in the plastic state in question; For this purpose, conventional mixers such as kneading machines, mixing mixers and (mixing) extruders can be used. If (mixed) polymer too high melting lamp-. In order to prevent mixing - due to the premature decomposition of the peroxide - it is recommended that, above all, epoxide groups should be attached to the solid (mixed) polymer by contacting with these peroxides, whereby the modified material is melted and the epoxide groups are homogeneously distributed.

Alternatively, the (mixed) polymer may be dissolved first, and the reaction with said peroxides may be performed in solution.

An important aspect of the use of the invention is that the moment at which the peroxide and the (mixed) polymer are contacted with each other and the moment at which the peroxide is to be decomposed can be selected independently of other conventional (mixed) polymer preparation steps. such as the addition of additives, molding, etc. First, for example, epoxide groups can be incorporated into a (mixed) polymer using peroxide and then additives can be added, after which the product can be molded. However, it is also possible, for example, to add peroxide to the (mixed) polymer together with other additives and to decompose the peroxide in the next molding step, such as extrusion, compression molding, blow molding or injection molding, at elevated temperature. The only restriction here is on certain (mixed) polymers which are ultimately intended to be crosslinked. In the case of such (se-15 ka) polymers, care should be taken that the peroxide is in any case present in the (mixed) polymer before crosslinking.

Examples of suitable (mixed) polymers which can be modified according to the invention with the aid of epoxide groups are saturated (mixed) polymers such as polyethylene, e.g. LLDPE, MDPE, LDPE and HDPE, polypropylene, both iso-tactical and atactic, ethylene / vinyl acetate ethylene / ethyl acrylate copolymer, ethylene / methyl acrylate copolymer, ethylene / methyl methacrylate copolymer; Capolymer, chlorinated polyethylene, fluoroelastomer, silicone rubber, polyurethane, polysulfide, polyacrylate rubber, ethylene / propylene copolymer, polyphenylene oxides, nylon, polyesters such as polyethylene terephthalate and polybutene phthalate, secarbonate, polycarbonate ), poly (butene-2), poly (isobutylene), poly (methylpentene), polyvinyl chloride, polyvinyl chloride / vinyl acetate graft copolymer, polyvinyl chloride / acrylonitrile graft copolymer, and combinations thereof; unsaturated (mixed) polymers such as polybutadiene, polyiso-35-ene, poly (cyclopentadiene), poly (methylcyclopentane-<9 92071 diene), partially dehydrochlorinated polyvinyl chloride-propylene-ethylene / styrene copolymer / butylene / styrene copolymer, acrylonitrile diene monomer terpolymer, isoprene / styrene copolymer, isoprene / isobutene copolymer, isoprene / styrene / acrylonitrile liter polymer, polychloroprene, butadiene / acrylonitrile copolymer, natural rubber compound, natural rubber Combinations of saturated and unsaturated polymers can also be modified according to the invention. In general, any 10 (mixed) polymers containing removable hydrogen atoms can be used in this process.

It has been found that contacting certain (mixed) polymers with these peroxides results in degradation of the myds polymer chains, which can affect the roecan properties of the modified (mixed) polymer.

In particular, those polymers which have a tendency to form tertiary carbon radicals under peroxide decomposition conditions tend to decompose. Examples of (mixed) polymers which are susceptible to degradation are poly-20 isobutene, poly (α-methyl) styrene, polymethacrylates, polymethacrylamide, polyvinylidene chloride, polypropylene, especially isotactic polypropylene, and polyvinyl alcohol. According to a preferred embodiment of the invention, this modification is carried out with the excipient ISsnS. Excipient, etc .; : 25 is generally milled as a polyfunctional reactive additive, e.g., it is a polyunsaturated compound used in the crosslinking of (mixed) polymers, which additive reacts very rapidly with polymeric radicals, overcomes steric hindrance effects and minimizes undesired side reactions. For more information on excipients, sometimes referred to as coactivators, see Rubber Chemistry and Technology, vol. 61, p. 238-254 and W. Hofmann, Progress in Rubber and Plastics Technology, vol. 1, No. 2, March 1985, p. 18-50. In connection with the inventor-35 tddn, the term "excipient" has the same meaning. A wide variety of excipients are commercially available, such as di- and triallyl compounds, di- and tri (meta) acrylate compounds, bismaleimide compounds, divinylbenzene, vinyltoluene, vinylpyridine, paraquinone dioxime, and 1,2-cis-polybutadiene thereof. In addition, oligomers or polymers of aromatic compounds containing at least two alkenyl substituents, such as oligomers of 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3,5-triisopropenylbenzene, should be mentioned. The addition of an effective amount of an excipient to the (mixed) polymer before or during the reaction with these peroxides avoids a deterioration in the mechanical properties and sometimes even improves. In addition, the use of this & an excipient provides improved adhesion of the resulting modified (mixed) polymers to substrates of a more polar nature. This improvement in the adhesion properties may be related to the better efficiency of the incorporation of the epoxide groups according to the invention when additional excipients are present. However, kek-20 rankings do not want to be bound by this theory. Also when modifying (mixed) polymers which are less susceptible to degradation, it proved advantageous to use an excipient during the modification reaction, since the coupling efficiency of the epoxide groups could be increased in this way. Such po- ·. . The 25 polymers that generally crosslink under the action of peroxides are, for example, polyethylene, atactic polypropylene, polystyrene, polyacrylates, polyacrylamides, polyvinyl chloride, polyamides, aliphatic polyesters, ethylene polyethylene, polyvinylpyrrolidone, saturated, Thanks to the invention, the advantageous effect on the physical and chemical properties due to the presence of epoxide groups, which has hitherto been limited to a relatively small group of (mixed) polymers (see recital 35 in the description), can now be achieved with a wide range of other (mixed) polymers. Particularly suitable (mixed) polymers for modification according to the invention are polyethylene, polypropylene and ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / propylene / diene monomer terpolymer.

The peroxide according to the invention is generally used in an amount of 0.01 to 15% by weight, preferably 0.1 to 10% by weight and preferably 1 to 5% by weight, based on the (mixed) weight of the polymer. Combinations of peroxides according to the invention can also be used. There may also be an advantage to the presence of another peroxide having a lower decomposition lamp than the peroxide of the invention.

The LSmpd state in which the modification is carried out is generally in the range of 50 to 350 ° C, preferably 100 to 250 ° C, care being taken to ensure that the duration of the modification step under given conditions is at least five peroxide half-lives to obtain optimum results.

As mentioned above, the (mixed) polymer may additionally contain conventional additives. Examples of such additives are stabilizers such as inhibitors against oxidative, thermist and UV degradation, lubricants, fillers and pH adjusters such as calcium carbonate, release agents, vS agents, reinforcing agents or non-reinforcing agents such as alumina, lime, soot and fibrous materials, coreSvSt substances, plasticizers, accelerators, crosslinkers such as peroxides and sulfur. These additives can be used in a conventional manner.

The invention is explained in the following examples. 30 så.

Example 1 2-Allylperoxy-2-methylpropane_perperoxide 11 '

To a mixture of 0.1 moles of powdered KOH, 35 0.02 moles of benzyltriethylammonium chloride and 100 ml of 12,92071 dichloromethane and stirred at 5-10 ° C was added a mixture of 0.1 moles of t -butyl hydroperoxide, 0.1 mol of allyl bromide and 70 ml of dichloromethane. After the temperature rose to 20 ° C, the reaction mixture was stirred for four hours at this temperature. After filtration, the dichloromethane solution was concentrated by evaporation under reduced pressure. To the residue was added 60 ml of pentane. The organic layer was washed three times with 15 ml of 10% by weight aqueous potassium hydroxide solution and then with water until the pH was 7. The organic layer was dried over anhydrous sodium sulfate and concentrated by evaporation under reduced pressure. 7.3 g of a colored liquid were obtained, containing 95% peroxide i: tS (determined by GLC).

Preparation of 3-allylperoxy-3,3-dimethylpropene (peroxide 2)

Peroxide 2 was prepared using the same procedure as shown for peroxide 1 except that 1,1-dimethyl-2-propenyl-20-hydroperoxide was used instead of t-butyl hydroperoxide.

After work-up, 11.0 g of a colorless liquid containing 91% of peroxide 2 (determined by GLC) were obtained.

Preparation of (1-allylperoxy-1-methyl-1-phenyl) ethane (peroxide 3): The procedure was the same as that shown for peroxide 1 except that (1-hydroperoxy-1-methyl-1-phenyl) ethane was used instead of t-butyl hydroperoxide. .

After work-up, 10.3 g of a colorless liquid with a peroxide 3 content of 86% (determined by GLC-30) were obtained.

Preparation of 2,5-dimethyl-2,5-di (allylperoxy) hexane feproxide 41

The preparation of peroxide 4 was carried out in an analogous manner to peroxide 1 using 0.05 mol of 2.5-35 dimethyl-2,5-dihydroperoxyhexane, 1.0 mol of allyl-13 92071 bromide and 35 ml of tetrahydrofuran. After the treatment, 8.4 g of a colored liquid with a peroxide 4 content of 62% as determined by GLC were obtained.

Prior to the modification experiments, peroxides 1-4 were further purified by column chromatography. After treatment, the concentration of each peroxide was determined by GLC. The structure of each peroxide 1-4 was confirmed by NMR and IR spectroscopic analyzes.

Table 1 gives the peroxide concentration and temperatures for each peroxide with decomposition half-lives of 10 hours, 1 hour and 0.1 hours (0.1 M solution in chlorobenzene).

Preparation of (1-meta-allylperoxy-1-roethyl-1-phenylethane (peroxide 5) A mixture of 0.11 moles of KOH, 11 ml of water and 0.005 moles of tetrabutylammonium chloride was stirred at 10 ° C. , a mixture of 0.10 moles of (1-hydroperoxy-1-methyl-1-phenyl) ethane was added over 30 minutes, and after the temperature had reached 20 ° C over 45 minutes, 25 ml of water was added. and the supernatant was separated, 50 ml of petroleum ether (60-80) was added to the organic layer, which was then washed twice with 100 ml of water, dried over anhydrous sodium sulfate and concentrated by evaporation under reduced pressure to give 19. 0 g of a colored liquid containing peroxide 5 84% (determined by GLC).

Preparation of (1- (2-butenyl) peroxy-1-methyl-1-phenyl) ethane (peroxide 6) Peroxide 6 was prepared using the same method as shown for peroxide 5 except that 2-butenyl bromide was used instead of t-butyl hydroperoxide.

19.9 g of a pale yellow liquid were obtained, containing 89% of peroxide 6 as determined by GLC.

14 92071

table 1

Peroxide Concentration% LampState (° C) to t% 10 hours 1 hour 0.1 ____ hours 1 95 113 133 156 5 2 91 100 123 149 3 95 108 128 149 4 95 103 125 150 5 84 104 122 143 6 89 113 129 147 10 a) 1 = 2-allylperoxy-2-methylpropane 2 = 3-allylperoxy-3,3-dimethylpropene 3 = (1-allylperoxy-1-methyl-1-phenyl) ethane 4 «2,5-dimethyl-2, 5-di (allylperoxy) hexane 5 - (1-meta-allylperoxy-1-methyl-1-phenyl) ethane 6 = (1- (2-butenyl) peroxy-1-methyl-1-phenyl) ethane.

gsiperKKl?

Polveteenin modification KMyttMen esimerkissM explaining one to six peroxide polyeteeniå 20 (Lupolen 1810H) was modified for 60 minutes in a 50 ml Brabender mixer at a speed of 30 rotor revolutions-per minute. The amount of peroxide in each experiment and the reaction temperatures are listed in Table 2. Table 2 gives the epoxide contents of the polymers obtained.

The epoxide content was determined as follows: In a 250 ml round bottom flask, about 1 g of product, weighed to the nearest one milligram, was dissolved in 100 ml of xylene at reflux. After the mixture was cooled to 30 ° C, 10.00 ml of 4 N HCl in 1,4-dioxane solution was added, after 30 mlS the mixture was kept at 50 ° C for 48 hours. Then 50 ml of acetone, 50 ml of water and 5 ml of 4 N nitric acid were added with stirring, after which the mixture was titrated potentiometrically with 0.01 N silver nitrate while stirring using a combined Ag, AgCl electrode.

15 92071

Table 2

Peroxide 4) Concentration Reaction Epoxide mmol / 100 g ISmpd content __pol .__ la ° C__mmol / 100 pol.

1 20 148-164 4.8 2 20 151-161 6.1 53 20 151-163 7.4 4 10 152-162 2.4 5 20 185 3.8 _6__20__174__3_j_5_ 10 a) for the identification of peroxides, see Table l.

Example 3 Modification of 2,6-dimethylpolyphenylene oxide with peroxide In a 1,300 ml open reactor, 11 g of 2,6-dimethyl-15-lipolphenylene oxide were mixed with 0.58 g of peroxide 1: tS, the total volume of the reaction mixture being adjusted to 100 ml: with monochlorobenzene. The duration of the treatment was six hours at 131 ° C, constant argon pressure.

The modified polymer was isolated by additional addition of the reaction mixture to petroleum ether (60-80) with vigorous stirring, after which the precipitated polymer was filtered. The resulting polymer was dried under vacuum for 17 hours at 70 ° C.

The epoxide content was determined as described in Example S2 and was found to be 11.0 mmol epoxy / 100 g polymer.

16 92071

Example 4

Modification of Polypropylene in the Presence of 1,3-Diisopropenylbenzene Oligomer Preparation of 1,3-diisopropenylbenzene oligomer To 498 g of 1,3-diisopropenylbenzene was added 1200 ml of heptane and 2 g of monocrystalline p-toluene sulfide were stirred, sulfonated 30 minutes at 80 ° C. The reaction mixture was then washed successively with 200 10 mL of 2 N NaOH and water until neutral. The organic layer containing heptane and unreacted 1,3-diisopropenylbenzene was evaporated at 100 ° C and 10 Pa. 169 g of a clear viscous oil were obtained.

Modification 15 Haake In an Rheomix * 500 electrically heated mixing chamber with a capacity of 53 g, the peroxide prepared according to Example 1 and oligo-1,3-diisopropenylbenzene were mixed with the mSSrSt polypropylene (Hostale * PPU 0180) given in Table 3. P, MFI (190 eC, 20 2/16 kg) to 6.3 g / 10 min, e.g. Hoechst) at 30 rpm and 15 min at 1 ° C at 180 ° C, giving the given peroxide and oligo-1,3-di -isopropylene benzene mSSrSt is calculated as a percentage by weight of polypropylene. During the reaction, the torque was recorded as a function of time on the Haake Record * system. 40, from which the vMan torque was obtained after 10 minutes (M10).

The modified polymer was granulated in a Retch * granulator using a 6 mm screen. Utilizing a Fonteyn * press, the granulate was formed on 1x125x200 mm sheets, 30 nylar polyester films under the following conditions: 1SmpStila 180 eC, 1 min without compression, 1 min 4-8 kPa, 3 min 41-61 kPa, 9 min cooling with water.

Tensile strength (TS) and elongation at break (EB) were measured according to ISO method R 257, using the Zwich * tensile tester 35 1474. In addition, a two-cored varnish varnish (2 K-17 92071 PUR Decklack, e.g. Akzo Coatings, 2 K-PUR Hardener , e.g., Akzo Coatings) according to ASTM D 429-81. The two-component coating was prepared by mixing 2 K-PUR Hardener with 2 K-PUR Decklack in a mixing ratio of 3: 1 in 5 parts by weight (pot life 8 hours). Application to nSytte by dip baling. Oven varnishing conditions were defrost time (20 ° C) = 10 min, body lamps i la 90 ° C, time 40 min. Test pieces measuring 130 x 25 mm were used with the other end coated with 10 1 cm of adhesive tape to which the coating was applied as described. A dip-coated polyamide gasket was used, and the coating was dried as described.

Exfoliation strength at 180 ° C was determined according to ASTM-D 429-81 using a Zwick tensile tester 1474 at a speed of 25 mm / min. The exfoliation strength also indicates the nature of the deterioration and is expressed as (average exfoliation force) / (patch size of the test pieces). Shear strength (LSS) was also measured using an epoxy resin having the following composition: 10 g of bisphenol A / F epoxy resins (Epikote * 20 DX 235, e.g. Shell), 6 g of polyaminoamide (Epilink 177, e.g. Akzo Chemicals) and 0.08 g of silane A 174 (e.g. Union Carbide). A thin resin film was applied to the adhesion surface (20x15 mm) of a sheet of modified polymer (40x20x1 mm). Another sheet made of modified polymer was placed over the adhesion surface, and the two parts were tightly pressed together to seal the air seals. This composition was kept in the oven for 72 hours at 30 ° C.

The shear strength was determined in a ZwickR tensile tester 30 1474 by measuring the force (kg / cm 2) required to separate the plates at a speed of 25 mm / min. If the adhesion gives up by fasting the two polymer pieces apart, the measured force is a measure of the adhesion of the epoxy resin. In the case that the polymer breaks before the adhesion 35 gives up, the force with which the adhesion gives up cannot be measured, but it is greater than the force required to break the polymer. The values obtained are shown in Table 3. The results of a comparative experiment carried out in the absence of 1,3-diiso-5-propenylbenzene oligomer are also shown.

Table 3

Peroxide oligo MIO TS EB LSS Exfoliating- “M-DIPB strength

n mmol / (tun- (mg) (MPa) (%) (kg / xlo'T

100 g nissa) cm3) (N / mm) poly- __merium_______ 598 41 40 0 1 ± 1 10 2 <50 ND2) ND2) -2) ND2) 3 10 2.5 538 23 30> 7.3υ 32 ± 1 4 __10__2.5 457 39 50> 9.4 ° 71 t 5 1) polymer breakage 15 2) el measurable

The values in Table 3 show that polypropylene modified without the ISS presence of diisopropenylbenzene is not suitable for further processing. Compared to unmodified polypropylene, the modified polypropylene has improved adhesion properties, which are pSS-relevant for the affinity of polypropylene lacquer, for the preparation of polymer blends, composites and curing agent-containing polymers.

Example 5 25 Adhesion-modified low density polyethylene (LDPE) LDPE (Lupolen 1810 H, MI (190 ° C, 2.16 kg) = 1.3 - 1.8 g / 10 min, e.g., by BASF.) Was modified with peroxide 3 and in another experiment with peroxide 4 as described in the first part of Example 2. Each polymer 30 obtained was compressed into a 1 mm thick sheet for 15 minutes at a lamp space of 160 ° C. Thereafter, the flaking strength and shear strength (LSS) of the two-component lacquer of each sheet using epoxy resin were measured in the same manner as described in Example 4, which also mentions the results of a comparative test performed without modification of LDPEs11S. The results clearly show that the adhesion obtained with the modified polymers according to the invention is higher than with the unmodified LDPE: 11S.

Table 4

Peroxide No. mmol / 100 g LSS Exfoliating strength __polymer__kg / cm2__x10O N / mm - 0 2.2 not at all 10 3 5 2.3 4 3 10 3.9 3 3 20 5.1 6 3 40 6.0 6 4 5 4.6 5 15 4 10 4.5 5 4 20> 4.9,} 12 4__40 __> 5.3 *> __ 12_ 1) degradation of the polymer

Claims (13)

20 92071 Patented applications A process for modifying (mixed) polymers using an organic peroxide, which process comprises contacting the peroxide with the (mixed) polymer and decomposing the peroxide, characterized in that the peroxide is an organic peroxide of the general formula H R? r3 10 'il 1 Process according to Claim 1, characterized in that R 1 is a hydrogen atom or a methyl group. ♦ 21 92071 Process according to Claim 1 or 2, characterized in that R 1, R 2, R 3 and R 4 are hydrogen atoms. Process according to Claim 1, characterized in that the peroxide is chosen from the group consisting of 3-allylperoxy-3,3-dimethylpropene, 3- (1-methyl-2-propenylperoxy) -3,3-dimethylpropene, 2-allylperoxy- 2-methylpropane, 2- (1-methyl-2-propenylperoxy) -2-methylpropane, 1-allylperoxy-1,1-di-10-methylbutane, 1-allylperoxy-1,1,3,3-tetramethylbutane , 1-allylperoxy-1,1-dimethyl-3-hydroxybutane, 1-allylperoxy-1,1-dimethylpropane, 1- (1-methyl-2-propenylperoxy) -1,1-dimethylpropane, 1- (1-allylpropoxy) roxy-1-methylethyl) -4-methylcyclohexane, (1- (2-methyl-2-propenylperoxy) -1-methylethyl) benzene, (1-allylperoxy-1-methylethyl) benzene, (1- (1- methyl-2-propenylperoxy) -1-methylethyl) benzene, (1- (2-cyclohexenylperoxy-1-methylethyl) benzene, 1,3-di (1-allylperoxy-1-methylethyl) benzene, 1,4 -di (1-allyl-20-peroxy-1-methylethyl) benzene, 1,3,5-tri (1-allylperoxy-1-methylethyl) benzene 1,2,5-di (allylperoxy) -2,5-dimethylhexane, 2,5-di (allylperoxy) -2,5-dimethyl-3-hexane. Process according to any one of Claims 1 to 4, characterized in that the amount of peroxide added is 0.01 to 15% by weight, the reaction temperature is 50 to 250 ° C and the duration of the modification step is five peroxide half-lives. Process according to Claim 5, characterized in that the amount of peroxide added is 0.1 to 10% by weight and the reaction temperature is 100 to 200 ° C. Process according to any one of claims 1 to 6, characterized in that the (mixed) polymer together with the excipient is contacted with said organic peroxide of formula (I). 22 92071 Process according to Claim 7, characterized in that the excipient is selected from the group consisting of di- and triallyl compounds, di- and tri (meth) acrylate compounds, bismaleimide compounds, divinyl compounds, polyalkenylbenzenes and their polymers, vinyltoluene , vinylpyridine, paraquinone dioxide, polybutadiene and their derivatives. Process according to Claims 1 to 7, characterized in that the organic peroxides used are polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / p-ropene / diene monomer terpolymer or 2,6-dimethylene modifying. Process according to any one of Claims 1 to 9, characterized in that the (mixed) polymer decomposes during the modification. R 10 - O - 0 - C - C = C R 1 R 4 - n where n = 1 or 2; R 1 is hydrogen, an alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms; R 2, R 3 and R 4 may be the same or different and are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms; R 1 and R 2, R 1 and R 3, R 1 and R 4, R 2 and R 3, R 2 and R 4 or R 3 and R 4 together form an alkylene group having 3 to 12 carbon atoms when n = 1, R = a t-alkyl group which is not or is substituted by hydroxyl groups and contains 4 to 18, preferably 4 to 12, carbon atoms, a t-alkenyl group having 5 to 18, preferably 5 to 12 carbon atoms, or a group of the general formula CH3 • K) '- ch3 v when n = 2, R = an alkylene group having 8 to 12 carbon atoms and having a tertiary structure in both pMs, or an alkynylene group having 8 to 12 carbon atoms and having a tertiary structure in both bases. Process according to any one of Claims 1 to 9, characterized in that the (mixed) polymer is crosslinked during the modification. Molded article, characterized in that it is made using a copolymer prepared by a method according to any one of claims 1 to 7. Molded article, characterized in that it is made using two or more (mixed) polymers, at least one of which is a (mixed) polymer produced by a process according to any one of claims 1 to 7. 23 92071