CA1326580C - Modification of (co)polymers employing organic peroxides - Google Patents

Abstract

ABSTRACT

Organic (co)polymers are modified by contacting them with an organic peroxide and decomposing the peroxide. To decompose also saturated (co)-polymers use is made of an organic peroxide having the general formula:
R-(O-O-CH1-CR2=CR3R4)N, wherein N is 1, 2 or 3; R1 is H, C1-C4 alkyl or C2-C4 alkylene; R2, R3 and R4 are, independently, H or C1-C4 alkyl; two of the substituents R1-R4 together may form C3-C12 alkylene; and, when N is 1, R is an optionally hydroxyl substituted C4-C18 T. alkyl, P-menth-8-YL, C5-C18 T.alkenyl, 1-vinylcyclohexyl or a group of the formula: -C(CH3)2-C6HJ(5-M)-R5(M), wherein M is O, 1 or 2 and R5 is isopropenyl or 2-hydro-xyisopropyl; when N is 2, R is a C8-C12 alkylene or alkynylene group having a tertiary structure at both ends, or a group having the formula:
-(C)CH3)2)2-C6H(4-X)-R5(X), wherein X is 0 or 1; and when N is 3, R is 1,2,4-or 1,3,5-triisopropylbenzene-alpha, alpha " -triyl, i.a., 3-allyl-peroxy-3,3-dimethylpropene according to a preferred embodiment the modi-fication is carried out in the presence of a coagent, whereby the advan-tageous polymer properties, sush as adhesion to polar materials, are further enhanced.

Description

The invention relates to a proce~s of modifying (co~polymers employing organic peroxides and to shaped objects comprising ` the modified (co)polymers.

It is generally known that the introduction of epoxide or other functional groups into tha appropriate (co)polymers may lead to improved physical and chemical properties of the (co)polymers. ~ccording ta Rubber World 191(6) pp. 15-20 (1935) and Rubber Developments, Vol. 38, No. 2, pp. 48-50 (1985), for instance, the introduction of epoxide groups into natural rubber leads to advantages such as an increased glass transition temperature, increased oil resistance~ reduced gas permeability, improved resilience, increased tensile strength, and improved adhesion to other materials, such as silica fillers, glass fibres and other polymers, more particularly PVC, which is of importance to the preparation of pol~meric blends. Further, the polymers thus modified per~it carrying out chemical reactions that are typical o~
epoxy groups. As examples thereof may be mentioned: i) cross-linking the polymer with polyfunctional compounds containing active hydrogen atoms, such as polyamines and dibasic acids, which is described in Chemical Reactions of Polymers, E.M. Fettes (ed.), Interscience Publications, New York ~1964), Chapter II, part E, pp. 152 et. seq., ii) covalently bonding to the polymer of antioxidants having amino groups in the molecule, which is described in Journal of Polymer Science, Polymer Letters Edition, VolO 22, 327-334 (1984) and iii~ reacting with fluorine-containing compounds, such as trifluoroacetic acid, resulting in a polymer with . , ~ , ~ .
, . : ::
, . - . .. . .

~ 1 ~26580 ... .

improved lubrici~y and ozon resistance, which is described in , W0 85/03477, published August 15, 1985.

~, Generally, epoxide groups are introduced into (co)polymers by so-called expoxidation reaction~, in which an unsaturated (co)polymer in the form of a latex or dissolved in an organic solvent is brought into reaction with an epoxidizing reagent suitable for unsaturated double bonds, such as a lower aliphatic peroxy carboxylic acid. To thi~ method, however, ~ 10 there are several disadvantages. First of all, the j r~quirement that the (co)polymer should be unsaturated implies that cnly a very limited number of (co)polymers can be provided with epoxide groups. For instance, the entire group of saturated (co)polymers is excluded ~rom being functionalized by that route. In the second place, the use of solvents implies that the epoxidakion reaction must be followed by a purification step. In addition, to the i, drawbacks to such a step from the point of view of processing technique there are the obvious disadvantages to the use of solvents from the poin~ of view of energy consumption and environment pollution. In the third place, the epoxidation reaction is always attended with side reactions, such as the . formation o~ hydroxyl groups, acyloxy groups, ether groups, keto groups and aldehyde groups, which detracts from the envisaged object of introducing epoxide groups.

~, Finally, it should be mentioned that it is known to prepare , epoxide groups-containing (co~polymers by copolymerizations ij and graft polymerizations with monomers containing a glycidyl i 30 group (cf. Journal of Polymer Science, Vol. 61, pp. 185 194 , - 2 -,~j '' . :

' , ' ~ ' 1 3265~0 ~`
~1962), Makromol. Chem., Rapid Commun. 7, pp. 143-148 (1~86) and Die Angewandte Makromolekulare Chemie 48, pp. 135-143 (197531. The inevitable attendant formation, however, of undesixable side products, such as the formation of homopol~mers of the glycidyl group-containing monomer, is considered a drawback in ac~ual praCtice. Moreover, these methods permit preparation of only a limited group of modified (co)polymers.

The invention provides a process employing particular organic peroxides for modi~ication of (co)polymers~ The organic peroxides correspond to the following formula R - 0 - 0 - C - C = C (I) l l4 n wherein n = 1, 2 or 3 Rl itands for hydrogen, an alkyl group having 1-4 carbon atoms or an alkenyl having 2-4 carbon atoms;
R2, R3 and R4 may be the same or different and represent `~ hydrogen atoms or alkyl groups containing 1-4 carbon atoms;
.~ Rl and R2, Rl and R3, R1 and R4, R2 and R3, R2 and R4, or R3 and R4 form an alkylene having 3-12 carbon atoms.

) - 2a -, ,. ~ ..
.. , ~
, .

,~ , ,. . :
.

`:

.

when n = 1 . R = a t-alkyl group substituted or not with a hydroxyl group and con- taining 4-18, preferably 4-12 carbon atoms, . p-menth-8-yl, a t-alkenyl group containing 5-18, preferdbly 5-12 carbon atoms, 1-vinylcyclohexyl or a group of the general formula .
CH

wherein m = C, 1 or 2 and R5 represents an isopropenyl group or a 2-hydroxyisopropyl group;

when n = 2, R = an alkylene group with 8-12 carbon atoms which at both ends has a tertiary structure, an alkynylene group with 8-12 carbon atoms which at both ends has a tertiary structure, a group of the general formula fH3 ~ fH3 c - 1- +~ c CH3 ~ CH3 R5x wherein x = 0 or 1 and R5 has the above-indicated meaning when n = 3 R = 1,2,4-triisopropy~benzene~ "-triyl or 1~3,5-triisopropylbenzene-a~ "-triyl;

The alkyl groups, alkenyl groups and alkylene groups may be linear or branched, unless otherwise indicated. In view of sterical requirements it should be noted that when there is an aromatic ring in the molecule (see :il ' ., above wi~h n = 1 and n = 2), the ring substituents must in the case of disubstitution not be in a position ortho relative to each other and in the case of trisubstitution not be in three adjacent positions.

It should be added that from Bull. Soc. Chim. France No. 2l 198-202 (1985) t-butyl allyl peroxide is known in itself and that mention is made in this publication of this peroxide being capable of 2,3-epoxypropanating organic solvents with labile hydrogen atoms. As solvents are mentioned cyclo-hexane9 tetrahydrofuran, propionic acid, propionic anhydride, methyl pro-pionate~ acetonitrile and chloroform. The article also mentions the need for the presence of an auxiliary initiator having a decomposition tempera-ture 10wer than that of the t-butyl allyl peroxide. But this article does not disclose the present invention.

From U.S. Patent Specification 2 516 649 compounds are known in themselves of the general formula ., ~ R1 - 0 - 0 - R2 wherein :,' R1 = a tertiary organic radical R2 = represents an unsaturated aliphatic or cyclic aliphatic radical, more particularly allyl tertiary-butyl peroxide, allyl tertiary-amyl per-oxide, allyl~ dimethylbenzyl peroxide, and me~hallyl tertiary-butyl peroxide~
According to said Patent Specification the above ally1 compounds may be used as catalysts for the polymerization of conjugated or non-conjugated ' polyunsaturated compounds.

J' The peroxides . .
The peroxides according to the invention correspond to the above-described formula (I) and are selected from the class of the dialkyl peroxides. They may be prepared in the usual manner. In preparing dialkyl peroxides use may be made of a primary or a secondary alkenyl deriva~ive of the general formula ` x - C - C = C (I I ) Rl l4 ..
:, ~.: ;:, . .

wherein R1-R4 have the above-indicated meaning and x represents Cl, Br, 0502CH3. -52- ~ - CH3 or a different leaving group.

As examples of suitable starting compounds may be mentioned:
- allyl bromide; (2-propenyl bromide), - 2-methyl-2-propenyl bromide; (methylallyl bromide)~
- 1-methyl-2-propenyl bromide, - 1-ethyl-2-propenyl bromide, - 1-propyl-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 On account of its readily being available use is preferably made of allyl bromide. In the preparation of the present dialkyl peroxides a primary or secondary alkenyl halide II can be reacted in a usual way in an alkaline medium with a hydroperoxide in the presence of a phase transfer catalyst.

As examples of suitable hydroperoxides may be mentioned:
- 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, diisopropyl-2-propenyl hydroperoxide, - t-butyl hydroperoxide, - 1,1-dimethyl butyl hydroperoxide, ,. ~

.. `

' ~

1 t 326580 ACD 2100 R
.. - 6 .. . .
- 1,1,3,3-tetramethyl butyl hydroperoxide, dimethyl-3-hydroxybutyl hydroperoxide, - t-pentyl hydroperoxide, - 1-ethenyl-1-hydroperoxycyclohexane, - 1-(1-hydroperoxy-1-methyl ethyl)-4-(1-hydroxy-1-methyl ethyl)benzene, - 1-(1-hydroperoxy-1-methyl ethyl)-4-methyl cyclohexane, - (1-hydroperoxy-1-methyl ethyl)benzene; ~-cumyl hydroperoxide), - 1,3-di(1-hydroperoxy-1-methyl-1-phenyl) ethane, - 1,4-di(1-hydroperoxy-1-methyl-1-phenyl) ethane, - 1,3,5-tri(1-hydroperoxy-1-methyl-1-pheny1) ethane, - 2,5-dimethyl-2,5-dihydroperoxyhexane, - 2,5-dimethyl-2,5-dihydroperoxy-3-hexyne.

~s typical examples of dialkyl peroxides for use according to the inven-tion may be mentioned:
- 3-allyl peroxy-3,3-dimethyl propene, - 3-(1-methyl-2-propenyl peroxy)-3l3-dimethyl propene, - 2-allyl peroxy-2-methyl propane, -.2-(1-methyl-2-propenyl peroxy)-2-methyl propane, - 1-allyl peroxy-l,l-dimethyl butane, - 1-allyl peroxy-1,1,3,3-tetramethyl butane, - l-allyt peroxy-1,1-dimethyl-3-hydroxybutane, - 1-allyl peroxy-1,1-dimethyl propane, - l-(l-methyl-2-propenyl peroxy)-1,1-dimethyl propane 9 - l-(l-allyl peroxy-1-methyl ethyl)-4-methyl cyclohexane, - (1-(2 methyl-2-propenyl peroxy)-l-methyl-l-phenyl) ethane, - (l-allyl peroxy-l-methyl-l-phenyl) ethane, - (1-(1-methyl-2-propenyl peroxy)-1-methyl-1-phenyl) ethane, - 1,3-di(l-allyl peroxy-1-methyl-1-phenyl) ethane, - 1,4-di(1-allyl peroxy-l-methyl-1-phenyl) ethane, - 1,3,5-tri(1-allyl peroxy-1-methyl-1-phenyl) ethane, - 2,5-di(allyl peroxy)-2,5-dimethyl hexane, - 2,5-di(allyl peroxy)-2,5-dimethyl-3-hexyne, - ~1-(2-cyclohexenyl peroxy-1-methyl-1-phenyl) ethane.

The peroxides can be prepared, transported, stored and applied as such or in the form of powders, granules, solutions, aqueous suspensions or emul-sions, pastes, etc.

, . ; , ;~ .

1 3265~0 . .
-~ Which of-these Forms is to be preferred partly depends on the ease of feeding the peroxide into closed systems. Also considerations of safety (desensitizing) may play a role. As examples of suitable desensitizing , agents may be mentioned solid carrier materials, such as silica, chalk and ~` clay, inert plasticizers or solvents, such as mono- or dichloro benzene, and water.

Modification of (co)polymers ,, The present peroxides are excellently suitable for use in the preparation of epoxide groups-containing (co~polymersj in which process a "non-modi-fied" lco)polymer is brought into contact with the peroxide; upon which the peroxide will be entirely or almost entirely deco~posed. The peroxide may be brought into contact with the (co)polymer in various ways, depen-ding on the object of the modification. If, for instance, epoxide groups are to be present on the surface of a (co)polymeric object, the peroxide may be applied to the surface of the material to be modified. It will often be desirable for epoxide groups to be homogeneously distributed in the (co)polymeric matrix. In that case the peroxide may be mixed with the material to be modified, which material may either be in the molten state, solution or, in the case of an elastomer~ in the plastic state; to this end use may be made of conventional mixers, such as kneaders, internal mixers and (mixing) extruding equipment. Should the mixing be impeded by a too high melting temperature of the (co)polymer -because of premature peroxide decomposition- it is recommended that first of all the (co)poly-mer in the solid state should be provided with epoxide groups by contac-ting with the present peroxides, after which the modified material is melted and the epoxide groups will be homogeneously distributed in the matrix. Alternatively the (co)polymer may be dissolved first, and the reaction with the present peroxides be carried in solution.
., .
j An important practical aspect of the invention is that the moment the ; peroxide and the (co)polymer ar~ brought into contact with each other and also the moment the peroxide is to be decomposed can be chosen indepen-dently of other usual (co)polymer processing steps, such as introducing additives, shaping, etc. First of all, for instance, epoxide groups may be introduced into a (co)polymer employing a peroxide and subsequently ad-ditives may be introduced, after which the product may be mould processed.
However, it is also possible, for instance, for the peroxide to be added , . , . , . . ~ . . -. . , ~ , . .
; :
.
:

..

to the (~o)polymer along with other additives and to decompose the per-oxide in a following shaping step at elevated temperature, such as extrusion, compression moulding, blow moulding or injection moulding.
The sole restriction here applies to certain (co)polymers which in the end are to be cross-linked. In the case of such (co)polymers care should be taken that the peroxide is in any case present in the (co)polymer prior to cross-linking.

Examples of suitable (co)polymers which according to the invention can be modified by means of epoxide groups are saturated (co)polymers9 such as polyethylene, e.g. LLDPE, MDPE, LDPE and HDPE, polypropylene, both iso-tactic and atactic, ethylene/vinylacetate copolymer, ethylene/ ethylacry-late copolymer, ethylene/methylacrylate copolymer, ethylene/methylrneth-acrylate copolymer9 chlorinated polyethylene, fluorrubber, silicone rubber, polyurethane, polysulphide, polyacrylate rubber, ethylene/propy-lene copolymer, polyphenylene oxides, nylon, polyesters, such as poly-ethylene terephthalate and polybutylene terephthalate, polycarbonates, copolyetheresters, poly~butene-1), poly(butene-2), poly(isobutene), poly-(methylpentene), polyvinyl chloride, polyvinyl chloride/vinylacetate graft copolymer, polyvinyl chloride/ acrylonitrile graft copolymer, and combi-nations thereof; and unsaturated (co)polymers, such as polybutadiene, polyisoprene, poly(cyclopentadiene), poly(methylcyclopentadiene), partly dehydrochloridated polyvinyl chloride, butadiene/styrene copolymer, acryl-onitrile/butadiene/styrene terpolymer, ethylene/propylene/dienemonomer terpolymer, isoprene/styrene copolymer, isoprene/isobutylene copolymer, isoprene/styrene/acrylonitrile terpolymer, polychloroprene, butadiene/-acrylonitrile copolymer, natural rubber, and combinations thereof. Also combinations of saturated and unsaturated polymers can be modified accor-ding to the invention. In general, any (co)polymer comprising abstrac-table hydrogen atoms can be employed in the present process.

It has been found that by contacting certain (co)polymers with the present peroxides also degradation of the polymer chains occurs, which may affect the mechanincal properties of the modified (co)polymer. Particularly those polymers prone to the formation of tertiary carbon radicals under the conditions of peroxide decomposition tend to undergo degradation. Examples of (co)polymers liable to degradation are polyisobutylene, poly(CL-methyl)-styrene, polymethacrylates, polymethacrylamide, polyvinylidene chloride, ., ' ~' .":; ' ' . ~ .

:
polypropylene, in particular isotactic polypropylene, and polyvinyl/alco-hol. According to a preferred embodiment of the invention the present mo-dification is conducted in the presence of a coagent. A coagent is gene-rally understood to be a usually polyfunctional reactive additive e.g. a polyunsaturated compound for use in cross-linking of (co)polymers, which additive will react very rapidly with polymer radicals, will overcome ste-ric hindrance effects and will minimize undesirable side reactions. For further information about coagents or sometimes called coactivators it is referred to Rubber Chemistry and Technology, Vol. 61, pp. 238-254 and W.
Hofmann, Progress in Rubber and Plastics Technology, Vol. 1, No. 2, March 1985, pp. 18-50. In relation to the present invention the expression "co-agent" has the same meaning. A wide variety of coagents is commercially available such as di-and triallyl compounds, di-and tri(meth)acrylate com-pounds, bismaleimide compounds, divinyl benzene, vinyl toluene9 vinyl py-ridine, parachinone dioxime, 1,2-cis-polybutadiene and their derivatives.
Furthermore, mention should be made of oligomers or polymers of aromatic compounds having at least two alkenyl substituents, such as oligomers of 1,3-diisopropenyl benzene, 1,4-diisopropenyl benzene, 1,3,5-triisoprope-nyl/benzene. Incorporating an effective amount of a coagent into the (co)-polyer prior to or during the reaction with the present peroxides, will avoid the reduction of the mechanical properties and sometimes even result in an improvement. Surprisingly this use of a coagent further provides an enhauced adhesion strength of the resulting modified (co)polymers to sub-strates of a more polar nature This enhancement oF the adhesive proper-ties may be attributable to a higher efficiency of the epoxide-groups in-troduction according to the invention, when additionally coagents are pre-sent. However, the inventors do not wish to be bound by this theory.
Also in modifying (co)polymers less liable to undergo degradation it appeared advantageous to include a coagent during the modification reaction, since the efficiency of the introduction of epoxide-groups could be increased in this way. Such polymers generally being cross-linked under the action of peroxides are, for example, polyethylene, atactic polypro pylene, polystryren, polyacrylates, polyacrylamides, polyvinylchloride, polyamides, aliphatic polyesters, polyvinylpyrrolidone, unsaturated rub-bers, polysiloxanes, ethylene propylene rubbers, ethylene propylene diene rubbers and their copolymers. Due to the invention the favourable effect on the physical and chemical properties as a resul~ of the presence of epoxide groups, which has so far been limited to a relatively small group , ~ : , ,. ~, - .

, :`

` ACD 2100 R

.
of (co)pslymers (see the introductory part of the description), can now also be obtained with d large group of other (co)polymers.
Particularly suitable (co)polymers to be modified by way of the invention are polyethylene, polypropylene, and ethylene/propylene copolymer, ethylene/vinylacetate copolymer, ethylene/propylene/dienemonomer terpoly-mer.
The peroxide according to the invention is generally used in an amount of 0,01 to 15% by weight, preferably ~,1 to 10% by weight, and more particu-larly 1 to 5% by weight, calculated on the weight of the (co)polymer. Use also may be made of combinations of peroxides according to the invention.
Also of advantage may be the presence of an auxiliary peroxide having a decomposition temperature lower than that of the peroxide according to the invention.
The temperature at which the modification is carried out is generally in the range of 50 to 350C, preferably 100 to 250C, care being taken then that in order to obtain optimum results the duration of the modification step under the given conditions is at least five half-life periods of the peroxide.
As mentioned above, the (co)polymer may in addition also contain usual additives. As examples of such additives may be mentioned: stabilizers, such as inhibitors against oxidative, thermal and UV degradation, lubri-cants, extender oils and pH controlling substances, such as calcium car-bonate, release agents, colorants, reinforcing or non-reinforcing fillers, such as silica, clay, chalk, carbon black and fibrous materials~ nuclea-ting agents, plasticizers, accelerators, crosslinking agents, such as per-oxides and sulphur. ~hese additives may be employed in the usual amounts.

The invention is further described in the following examples.

Example 1 Preparation of 2-allyl peroxy-2-methyl propane (peroxide 1) To a mixture of 0,1 mole of powdered KOH, 0,02 moles of benzyl triethyl ammonium chloride and 100 ml of methylene chloride stirred at 5-10C was added over a period of 35 minutes a mixture of 0,1 mole of t-butyl hydro-peroxide, 0,1 mole of allyl bromide, and 70 ml of methylene chloride.
After the temperature had increased to 20C, the reaction mixture was .

, . - . .
,. : . :........ . .

stirred for 4 hours at this temperature. Following filtration the methylene chloride solution was concentrated by evaporation under reduced pressure. To the residue were added 60 ml of pentane. The organic layer was washed three times with 15 ml of an aqueous solution of 10% by weight of potassium hydroxide and then with water to pH 7. The organic layer was dried with anhydrous sodium sulphate and concentrated by evaporation under reduced pressure. Obtained were 7,3 9 of colourless liquid having a peroxide 1 content determined by G.L.C. of 95%.
:, Prepa_ation of 3-all~l peroxy-3,3-dime~hyl prop ne (peroxide 2) The peroxide 2 was prepared using the same procedure as described for peroxide 1, except that use was made of 1,1-dimethyl-2-propenyl hydroper-oxide instead of t-butyl hydroperoxide.
Obtained after treatment were 11,0 9 of colourless liquid having a per-oxide 2 content determined by G.L.C. of 91%.
, Preparation of ~l-allyl peroxy-1-methyl-1-phenyl) ethane (peroxide 3) The procedure was the same as described for peroxide 1, except that use was made of ~l-hydroperoxy-1-methyl-1-phenyl) ethane instead of t-butyl hydroperoxide.
Obtained after treatment were 10,3 g of colourless liquid having a per-oxide 3 content determined by G.L.C. of 86%.

Preparation of 2,5-dimethyl-2,5-di(allyl peroxy)hexane (peroxide 4) The preparation of peroxide 4 was carried out in a manner analogous to that for- peroxide 1, use being made of 0,05 moles of 2,5-dimethyl-2,5-di-hydroperoxyhexane, 1,0 mole of allyl bromide, and 35 ml oF tetrahydro-furan. Obtained after treatment were 8,4 9 of colourless liquid having a peroxide 4 content determined by G.L.C. of 62%

Prior to the modification tests the peroxides 1-4 were further purified by column chromatography. After treatment the content of each of the per-oxides was determined by G.L.C. Of each of the peroxides 1-4 the structure was confirmed by NMR and IR spectroscopic analyses.

. , .

;- 12 1 326580 Table I gives for each peroxide the peroxide content and the temperatures at which the half-life periods of decomposition are 10 hours, 1 hour, and - 0,1 hour (0,1 M solution in chlorobenzene).
~, .
Prepdration of (1-methallylperoxy-1-methyl-1-phenyl) ethane (peroxide 5) To a mixture of 0,11 moles of KOH, 11 ml water and 0,005 moles of tetra-butyl ammonium chloride stirred at 10C was added over a period of 30 minutes a mixture of 0,10 moles (1-hydroperoxy 1-methyl-1-phenyl) ethane.
After the temperature had been increased to 20C over a period of 45 minutes, 25 ml of water were added and the organic supernatant layer was separate off. To the organic layer were added 50 ml of petroleum ether (60-80) followed by two washings with 100 ml water. The organic layer was dr~ed with anhydrous sodium sulphate and concentrated by evaporation under reduced pressure. Obtained were 19.0 g of colourless liquid having a per-oxide 5 content determined by G.L.C. of 84%.
~',` . .
~'~,! Preparation of (1-cro~ylperoxy-1-methyl-1-phenyl) ethane (peroxide 6) "
The peroxide 6 was prepared using the same procedure as described for peroxide 5, except that use was made of crotyl bromide instead of t-butyl-, hydroperoxide.
:, Obtained were 19,9 9 of pale yellow liquid having a peroxide 6 content , dermined by 6.L.C. of 89%.

, ;~ Table 1 ,:j Peroxidea) Content Temperature (C) for t2 f , % _ . ~.
10 hours 1 hours 0,1 hour ,.~ .__ _ ~ . _ ~ 9~ 113 129 147 . .

~: ,.; ' , , , . ~
~ . : ~ . i .. . . ..
. . .

~ ` - 1 326580 ACD 2100 R

.
a) 1=2-a1lyl peroxy-2-methyl propane 2=3-allyl peroxy-3,3-dimethyl propene 3=~1-allyl peroxy-1-methyl-1-phenyl) ethane 4=2,5-dimethyl-2,5-di(allyl peroxy)hexane 5=(1-methallylperoxy-1-methyl-1-phenyl) ethane 6=(1-crotylperoxy-1-methyl-1-phenyl) ethane.
Example _ Modification of polyethylene Use bein~ made o~ the 6 peroxides described in Example I, polyethylene A (Lupolen~r1810H) was modified in a 50 ml-Brabender blender at a speed of 30 rotor revolutions per minute for 60 minutes. The amount of peroxide in each exper;ment and the reaction temperatures are listed in Table 1. Table 2 also gives the epoxide contents of the resulting polymers.

The epoxide content was determined as follows:
In a 250 ml-round bottomed flask about 1 9 of product, which had been weighed out to the nearest 1 mg, was dissolved with refluxing in 100 ml of xylene. After the mixture had been cooled to 30C, 10,00 ml of a solution in 1,4-dioxane of 4N HCl were added, after which the mixture was kept at 50C for 48 hours. Subsequently, 50 ml of acetone, 50 ml of water and 5 ml of 4N nitric acid were added with stirring, after which the mixture was titrated poten$iometrically, with stirring, with 0,01 N silver nitrate, use being made of a combined Ag, AgCl electrode.

Table 2 . .
~ ~ __ Peroxidea) oncentration Reaction tem- Epoxide content mmoles/100 g pol. perature C mmoles/100 9 pol.
. __ - _ ..... . . ,,_ 1 20 148-164 4,8 2 20 151-161 6,1 3 20 151-163 7,4 4 10 152-162 2,4 185 3,8 6 20 174 3'5 a) for indentification of the peroxides, see table 1.

. .
: ~, :

` ~ 1 3 2 6 5 8 0 ~CD 2100 R

.
Example 3-Modification of 2,6-dimethyl-polyphenylene oxide with peroxide 1 , .
In a 300 ml open reactor 11 9 of 2,6-dimethyl-polyphenylene oxide were mixed with 0,58 9 peroxide 1, which reaction mixture was made up to a total volume of 100 ml with monochloro benzene. The duration of the treat-ment was 6 hours at a temperature of 131C under continuous argon pres-sure.
The modified polymer was isolated by adding the reaction mixture to vigo-rously stirred petroleum ether (60-80) followed by filtration of the pre-cipitated polymer. The polymer obtained was vacuum-dried for 17 hours at 70 C.
The epoxide content was determined as described in Example 2 and was found to be 11.0 mmoles of epoxy /100 g polymer.

Example 4 /
;~ Modification of polyprop~ene in the presence of 1,3-diisopropenyl benzene , oligomer ,1 .
- Prepar_tion of 1,3-diisopropenyl benzene oligomer To 498 9 of 1,3-diisopropenyl benzene were added 1200 ml of heptane and 2 9 of p-toluene sulfonic acid 1 aq followed by stirring for 30 min. at i 80C. Thereupon the reaction mixture was successively washed with 200 ml ; of NaOH 2N and water until neutral. The organic layer containing heptane and non-reacted 1,3-diisopropenyl benzene was evaporated at 100C and 0,1 mbar. Obtained were 169 g of clear viscous oil.

- Modification In a Haake Rheomix~ 500 electrically heated mixing chamber with a capacity of 53 9 the peroxide as prepared in Example 1 and oligo-1,3-diisopropenyl benzene were intermixed in the amounts given in Table 3 with polypropylene ~Hostalen0 PPU 0180 P, MFI (190C; 2,16 kg) = 6,3 9/10 min, ex. Hoechst) at a speed of 30 rpm and over a period of 15 min. at a temperature of 180C, the given amounts of peroxide and oligo-1,3-diisopropylen benzene . ~ :

~ ' "' ' ' .: `
: ; . , t 326580 being ca~culated on the percentage by weight of polypropylene. During the reaction torque versus time was registrated with a Haake Reocord~ system 40 from which the torque-after-10 minutes (M10) was derived.
The modified polymer was granulated in a Retch~ granulator by using a 6 mm sieve. Use being made of a Fonteyn~ press the granulate was formed into 1x125x200 mm plates between nylar polyester foil under the following con-ditions: temp. 180C; 1 min. without pressure; 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 in con-formity with IS0 method R 257, use being made of a Zwich~D tensile tester 1474. Moreov~er~ the peel strength of a b~ component lacquer (2 K-PUR Deck-lack~ex Akzo Coatings, 2 K-PUR Hardener, ex Akzo Coatings) was determined according to ASTM D 429-81. The two component coating was prepared by mixing the 2 K -P UR-Hardener~with 2 K-PUR-Decklack in a mixing ration 3:1 parts per weight (pot-life - 8h). Application to sample by dip coating.
Stovlng conditions were flash off time (20C)=10 min; object temperature 90C; time 40 min. Test pieces of dimensions 130 mmx25 mm were used one end being covered with 1 cm adhesive tape, whereupon the coating was applied as described. A dip coated polyamide gasket was applied and the coating was dried as described.
The 180 peel strength was determined according to ASTM-D 429-81 using a Zwick~tensile tester 1474 at. 25 mm/min. Besides indicating the nature of failure the peel strength is reported as (average peel force)/(diameter test pieces). Also the lap shear strenght (LSS) was measured using an epoxy resin having the following composition: 10 9 of bisphenolJ/F epoxy resins (Epikote~ DX 235, ex Shell), 6 9 ~f polyaminoamide (Epillnk~ 177;
ex. Akzo Chemicals) and 0.08 9 of silan A 174 (ex. Union Carbide). A thin film of resin was applied to the adhesion surface area (20x15 mm) of a modified polymer plate (40x20xl mm). Another modified polymer plate was placed on the adhesion surface area and the two parts were firmly cl amped together to avoid occlusion of air. This composition was kept in a stove for 72 hours of 30C.
The lap shear strenght was determined in a Zwick~ Tensile tester 1474 by measuring the force (kg/cm2) needed to separate the plates from each other at a speed of 25 mrn/min. In case the adhesion fails by shifting apart of the two pieces of polymer, the measured force is a measure for adhesion of the epoxyresin. In case the polymer breaks before the adhesion fails the force at which the adhesion will fail is not measurable but it will be ~ ~A fr P ~ ~ K

,: .. ~ , .

,, ~ .
`

~ 16 , . . .
higher th~n the force needed for polymer breakage. The values obtained are : given in Table 3. Also given are the results of a comparative experiment conducted in the absence of the 1,3-diisopropenyl benzene oligomer.

, .
.. . .
Table 3 _ _ .
Per oxide_ _ oligo M-DIPB M10 TS FB LSS Pe~l strength : nr. m100lf (phr~ (mg) ~MPa~ (%) ~kglcm2)x10-2 (N/mm) _ polymer _ _ _ ~ 598 41 40 3 1 + 1 2 _ ~50 ND2) N~2) 2j~1) ND2) -3 20 2.5 538 23 30 >7.31) 32 + 1 4 ~0 ~.5 457 39 50 >9.4 71 ~ 5 1) polymer breakage 2) not measurable :

From the values of Table 3 it will be clear that polypropylene modified in the absence of diisopropenyl benzene is not suitable to be further proces-sed. As compared with unmodified polypropylene the modified polypropylene displays improved adhesion properties which are of major importance to the affinity for paint of polypropylene, the production of polymer blends, composites and filled polymers.

Example 5 Adhesion to modified low density polyethylen ~LDPE) LDPE (Lupolen 1810 H, MFI ~190C; 2.16 kg) = 1,3-1.8 9/10 min, ex BA8F) was modified with peroxide 3 and in another experiment with peroxide 4 in the way described in the first part of Example 2. Each resulting polymer ~ ~ .

. ~.. : . . . .

:.~ 17 .
was compressed into a plate 1 mm thick over a period of 15 min. and at a temperature of 160C. Subsequently, of each plate the peel strength of d bi-component lacquer and the lapshear strenght (LSS) using an epoxy resin was measured in the way described in Example 4, which also mentions the results of a comparative experiment conducted with unmodified LDPE. The results clearly show that the adhesion obtained with modified polymers according to the invention is greater than that with unmodified LDPE.

. Table 4 ;-, ,., ., _ . __ Pero ~ide __ _ _ .

.~ nr. mmol/100 9 . LSS Peel strength polymer ~9/~ xlO-2 N/mm 0 2.2 nihil . 3 5 2.3 4 .- 3 10 3.9 3 .Z 3 20 5.1 6 3 40 6.Q 6 4 5 4.6 5 .1 4 10 4.5 5 . 4 20 >4.9 1) 12 Y 4 40 >5,3 1) ~ 1) polymer breakage . :: . , .: : , :
.

Claims (14)

1. A process for modifying (co)polymers employing an organic peroxide, in which process the peroxide is brought into contact with the (co)poly-mer and the peroxide is decomposed, characterized in that the peroxide is an organic peroxide of the general formula (I) wherein n = 1, 2 or 3 R1 stands for hydrogen, an alkyl group having 1-4 carbon atoms or an alkenyl having 2-4 carbon atoms;
R2, R3 and R4 may be the same or different and represent hydrogen atoms or alkyl groups containing 1-4 carbon atoms, R1 and R2, R1 and R3, R1 and R4, R2 and R3, R2 and R4, or R3 and R4 jointly form an alkylene having 3-12 carbon atoms.

when n = 1 R = a t-alkyl group substituted or not with a hydroxyl group and con-taining 4-18 carbon atoms, p-menth-8-yl, a t-alkenyl group containing 5-18 carbon atoms, 1-vinylcyclohexyl or a group of the general formula wherein m = 0, 1 or 2 and R5 represents an isopropenyl group or a 2-hydroxyisopropyl group;

when n = 2, R = an alkylene group with 8-12 carbon atoms which at both ends has a tertiary structure, an alkynylene group with 8-12 carbon atoms which at both ends has d tertiary structure, a group of the general formula wherein x = 0 or 1 and R5 has the above-indicated meaning when n = 3 R = 1,2,4-triisopropylbenzene-.alpha.,.alpha.',.alpha."-triyl or 1,3,5-triisopropylbenzene-.alpha.,.alpha.',.alpha."-triyl.

2. A process according to claim 1, characterized in that R1 is a hydrogen atom or a methyl group.

3. A process according to claim 1, characterized in that R1, R2, R3 and R4 are hydrogen atoms.

4. A process according to claim 1, characterized in that for n=1, R contains 4-12 carbon atoms when it is a t-alkyl group and R contains 5-12 carbon atoms when it is t-alkenyl group.

5. A process according to claim 1, characterized in that the peroxide is selected from the group of 3-allyl peroxy-3,3-dimethyl propene, 3-(1-methyl-2-propenyl peroxy)-3,3-dimethyl propene, 2-allyl peroxy-2-methyl propane, 2-(1-methyl-2-propenyl peroxy)-2-methyl propane, 1-allyl peroxy-1,1-dimethyl butane, 1-allyl peroxy-1,1,3,3-tetramethyl butane, 1-allyl peroxy-1,1-dimethyl-3-hydroxybutane, 1-allyl peroxy-1,1-dimethyl propane, 1-(1-methyl-2-propenyl peroxy)-1,1-dimethyl propane, 1-(1-allyl peroxy-1-methyl ethyl)-4-methyl cyclohexane, (1-(2-methyl-2-propenyl peroxy)-1-methyl ethyl)benzene, (1-allyl peroxy-1-methyl ethyl)benzene, (1-(1-methyl-2-propenyl peroxy)-1-methyl ethyl)benzene, (1(2-cyclohexenyl peroxy-1-methyl ethyl)benzene, 1,3-di(1-allyl peroxy-1-methyt ethyl)benzene, 1,4-di(1-allyl peroxy-1-methyl ethyl)benzene, 1,3,5-tri(1-allyl peroxy-1-methyl ethyl)benzene, 2,5-di(allyl peroxy)-2,5-dimethyl hexane, and 2,5-di(allyl peroxy)-2,5-dimethyl-3-hexyne,

6. A process according to any one of claims 1-5, characterized in that the added amount of peroxide is 0.01 to 15% by weight, the reaction temperature is 50 to 250°C, and the duration of the modification step is at least five half-life periods of the peroxide.

7. A process according to claim 6, characterized in that the added amount of peroxide is 0.1 to 10% by weight and the reaction temperature is 100-200°C.

8. A process according to any one of the claims 1-5 or 7, wherein the (co)polymer together with a coagent is brought into contact with said organic peroxide of the formula (I).

9. A process according to claim 8, wherein the coagent is selected from the group of di- and triallyl compounds, di- and tri-(meth)acrylate compounds, bismaleide compounds, divinyl compounds, polyalkenylbenzenes and their polymers, vinyl toluene, vinyl pyridine, parachinone dioxime, polybutadiene and their derivatives.

10. A process according to any one of claims 1-5, 7 or 9, characterized in that the organic peroxides are employed for the modification of polyethylene, polypropylene, ethylene/propylene copolymer, ethylene/vinylacetate copolymer, ethylene/propylene/dienemonomer terpolymer or 2,6-dimethyl-polyfenyleneoxide.

11. A process according to any one of the claims 1-5, 7 or 9, wherein the (co)polymer is degraded during the modification.

12. A process according to any one of the claims 1-5, 7 or 9, wherein the (co)polymer is cross-linked during the modification.

13. A shaped object manufactured using a copolymer prepared by the process according to any one of claims 1-5, 7 or 9.

14. A shaped object manufactured using two or more (co)polymers, of which at least one is a (co)polymer prepared by the process according to any one of claims 1-5, 7 or 9,.