JPH021703A - Modification of polymer by using organic peroxide - Google Patents

Abstract

PURPOSE: To reform the physical and chemical properties of a polymer by brining a specified organic peroxide containing aryl group into contact with a polymer or copolymer to decompose it, and introducing an epoxy group to a saturated polymer without using a solvent or causing a sub-reaction.

CONSTITUTION: An organic peroxide represented by the formula I [n is 1, 2 or 3; R¹ is H, C_1-4 alkyl or C_2-4 alkenyl; R²-R⁴ are H or C_1-4 alkyl; optional two of R₁-R₄ may be combined to form C_3-12 alkylene; and R is C_4-18 (substituted) t-alkyl, p-ment-8-yl, C_5-18 t-alkenyl, 1-vinylcyclohexyl, the formula II (m is 0, 1 or 2; R⁵ is isopropenyl or the like), or the formula III (X is 0 or 1)] (e.g.: 3-arylperoxy-3,3-dimethylpropene or the like) is brought into contact with a polymer (e.g.: polyethylene or the like) or copolymer. This peroxide is decomposed and reacted, whereby the polymer is reformed.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for modifying a polymer or copolymer (hereinafter simply referred to as polymer) using an organic peroxide, and a molded article containing the modified polymer.

incorporating epoxides or other functional groups into a suitable polymer;
It is widely known that the physical and chemical properties of polymers can be improved.

Rubber World 191(6), 15
~20 pages (1985) and Rubber Dev
elopments, Volume 38, No. 2. 48～
According to page 50 (1985), for example, introducing epoxide groups into natural rubber increases the glass transition temperature,
Increased oil resistance, reduced gas permeability, improved elasticity, increased tensile strength, and other materials such as silica fillers, glass fillers, and other polymers, especially PVC C
This results in benefits such as improved adhesion to (which is important in the production of polymer formulations). Furthermore, polymers modified in this way allow the epoxy groups to undergo typical chemical reactions. Examples of these include i) crosslinking the polymer with polyfunctional compounds containing active hydrogen such as polyamines and dibasic acids (this is
lons of Polymers, E, M, Fet
tcs (editor) S Interscience P
publications, New York (1984
2), Chapter 2, Part E, pages 152 et seq.), ii) Covalent bonding of antioxidants having amino groups in the molecule to polymers (this is described in the Journal
of Polymer 5science, Polym
erLetters Edition, Volume 22,
327-334 (1984)) and 111) with a fluorine-containing compound such as trifluoroacetic acid to yield a polymer with improved antifriction and ozone resistance. is a Swiss patent (
WO) 85/03477).

Generally, epoxide groups are introduced into polymers by so-called epoxidation reactions. In this reaction, an unsaturated polymer in the form of a latex or dissolved in an organic solvent is reacted with an epoxidizing reagent suitable for unsaturated double bonds, such as a lower aliphatic peroxycarboxylic acid. However, this method has some drawbacks.

First of all, the requirement that the polymer should be unsaturated means that only a very limited number of polymers can be provided with epoxy groups. for example,
Not all saturated polymers can be functionalized in this way. Second, since a solvent is used, the epoxidation reaction must be followed by a purification step.

In addition to the disadvantages of such processes from the point of view of processing technology, there are obvious disadvantages of the use of solvents from the point of view of energy consumption and environmental pollution. Thirdly, epoxidation reactions are always accompanied by side reactions such as the formation of hydroxyl, acyloxy, ether, keto and aldehyde groups which defeat the intended purpose of introducing epoxide groups.

Finally, it should be mentioned that it is known to prepare polymers containing epoxide groups by copolymerization and graft polymerization with monomers containing glycidyl groups (Journal of Polymer Sci.
nce, Vol. 61, pp. 185-194 (1
962).

Makromol, Chem, Rapid Co
mmun, 7. pages 143-148 (1986) and Die An, gewante Makromol
ekulare Chemie 48.135-143
(see Page (1975)). However, the unavoidable formation of undesirable by-products, such as the formation of homopolymers of monomers containing glycidyl groups, is considered to be a drawback in practice. Furthermore, these methods allow the production of only a limited group of modified polymers.

The present invention aims to obviate the aforementioned drawbacks of the known methods of introducing epoxide groups into polymers. To this end, we provide a method of using special organic peroxides to modify polymers.

The organic peroxide corresponds to the following formula:

In the formula, n=1.2 or 3; R1 means hydrogen, an alkyl group having 1 to 491 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms; R2, R3 and R4 are the same - or can be different groups and represent a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms; R and R2, R1 and r<3. R1 and R4R and R3
, R2 and R4, or R3 and R4 may form an alkylene group having 3 to 12 carbon atoms, if n=1, R is substituted or unsubstituted with a hydroxyl group, tert-alkyl radicals having 4 to 18, preferably 4 to 12 carbon atoms, p-mend-8-yl, t-alkenyl having 5 to 18, preferably 5 to 12 carbon atoms, 1- vinylcyclohexyl, or a group having the general formula benyl group or 2-hydroxyinpropyl group), and when n=2, R has 8 to 12 carbon atoms with a tertiary structure at both ends. alkylene group, an alkynylene group having 8 to 12 carbon atoms with a tertiary structure at both ends, a group having the general formula (%), and when n = 3, R is 1,2.4- Triisopropylbenzene-α.

α′, α″-triyl or 1.3.5-triisopropylbenzene-α, α′α
″-triyl.

Alkyl, alkenyl and alkylene groups can be straight chain or branched unless otherwise specified. In view of the steric requirements of atomic arrangement, when there is an aromatic ring in the molecule (see the cases where n = 1 and n = 2 above), the substituents on the ring are in mutually ortho positions in the case of disubstitution. It should be noted that, in the case of substitution, there must not be three adjacent positions.

t-Butyl allyl peroxide Bull, Soc.

Chin, France N (12,198-20
2 (1985) and that this publication states that this peroxide can be a 2,3-epoxypropanated organic solvent with reactive hydrogen atoms. Should. As solvents, mention may be made of cyclohexane, tetrahydrofuran, propionic acid, propionic anhydride, methylpropionate, acetonitrile and chloroform. The document also states that the presence of a co-initiator having a lower decomposition temperature than t-butyl allyl peroxide is required. However, this document does not disclose the present invention.

General formula % Formula % (wherein R1 is a tertiary organic radical and R2 is an aliphatic or cycloaliphatic radical, especially allyl tertiary-butyl peroxide, allyl secondary-amyl peroxide, allyl-α, α-dimethylbenzyl peroxide and methallyl sec-butyl peroxide) are known per se from US Pat. No. 2,516,649.

According to this patent specification, the allyl compounds can be used as catalysts for the polymerization of conjugated or non-conjugated polyunsaturated compounds.

Peroxide The peroxide of the present invention corresponds to formula (I) above and is selected from the species of diallyl peroxides. They can be manufactured in conventional manner. In the production of dialkyl peroxides, the general formula % formula % (wherein R1-R4 have the meanings given above and X is Cf
l, Sr, 03O2CH3.

It is possible to use primary or secondary alkenyl derivatives of

Examples of suitable starting materials include allyl bromide (2-propenyl bromide), 2-methyl-2-propenyl bromide (methyl allyl bromide), 1-methyl-2-propenyl bromide, 1-ethyl-2-propenyl promid,
1-propyl-2-propenyl bromide, 1-isopropyl-2-propenyl bromide, 2-t-butyl-2-
Propenylbromide, 2-neopentyl-2-propenylbromide, 2-butenylbromide, 1-methyl-2-
Butenyl bromide, 3-methyl-2-butenyl bromide, 2,3-dimethyl-2-butenyl bromide, 1,2.
Examples include 3-trimethyl-2-butenyl bromide and 2-cyclohexyl bromide.

Preferably, allylpromide is used because of its ease of handling. In the preparation of this diallyl peroxide, the primary or secondary alkenyl halide (1) can be reacted with the hydroperoxide in the presence of a phase transfer catalyst in an alkaline medium in a conventional manner.

Examples of suitable hydroperoxides include 1,1-dimethyl-2-propenyl hydroperoxide, 1-methyl-2-propenyl hydroperoxide,
1-ethyl-2-pyrobenyl 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 hydroperoxide, 1.1
, 3,3-tetramethylbutyl hydroperoxide, 1
．． 1-Dimethyl-3-hydroxybutyl hydroperoxide, t-pentyl hydroperoxide, 1-ethynyl-1-hydroperoxycyclohexane, 1-(1-hydroperoxy-1-methylethyl)-4~ (1-hydroxy-1- methylethyl)benzene, 1-(1-hydroperoxy-1-methylethyl)-4-methylcyclohexane, (1-hydroperoxy-1-methylethyl)benzene [α-cumylhydroperoxide], 1,
3-di(1-hydroperoxy-1-methyl-1-phenyl)ethane, 1,4-di(1-hydroperoxy-1
-Methyl-1-phenyl)ethane, L, 3.5-)su(1-hydroperoxy-1-methyl-1-phenyl)
Mention may be made of ethane, 2,5-dimethyl-2,5-dihydroperoxyhexane, and 2,5-dimethyl-2,5-dihydroperoxy-3-hexane.

Typical examples of dialkyl peroxides used in the present invention include 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-dimethylbutane, 1-allylperoxy-1,1,3,3-tetramethyl Butane, 1-allylperoxy-1,1-dimethyl-3-hydroxybutane, 1-allylperoxy-1,1-dimethylpropane,
1-(1-methyl-2-propenylperoxy)-1,
1-dimethylpropane, 1-(1-allylperoxy-
1-methylethyl)-4-methylcyclohexane, (1
-(2-methyl-2propenylperoxy)-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-methyl-1-phenyl)ethane, 1,4-di(1-
Allylperoxy-1-methyl-1-phenyl)ethane, 1.3.5-)ly(1-allylperoxy-1
-Methyl-1-phenyl)ethane, 2,5-di(allylperoxy)-2,5dimethylhexane, 2,5-di(
Examples include allylperoxy)-2,5-dimethyl-3-hexyne and (1-(2-cyclohexenylperoxy)-1-methyl-1-phenyl)ethane.

These peroxides can be manufactured, transported, stored,
They can be applied as such or in the form of powders, granules, solutions, aqueous suspensions or emulsions.

These forms are preferred in some respects because of the ease with which peroxide can be supplied to a closed system.

Moreover, it can perform one function in consideration of safety (desensitization). As suitable desensitizers, mention may be made of solid carrier substances such as silica, chalk and clay, inert plasticizers or solvents such as mono- or dichlorobenzene and water.

Modification of Polymers The peroxides described above are very suitable for the production of polymers containing epoxide groups. In the manufacturing method, unmodified polymer is contacted with peroxide. After contacting, the peroxide is completely or almost completely decomposed. The peroxide can be contacted with the polymer in a variety of ways depending on what is being modified. For example, if epoxide groups are present on the surface of a polymer object, peroxide can be applied to the surface of the material to be modified. It is often desirable for the epoxide groups to be uniformly dispersed throughout the polymer matrix. In that case the peroxide can be mixed with the substance to be modified.

The material can be either a molten solution or, in the case of an elastomer, a plastic state. Customary mixers can be used for this purpose, such as kneader 1 internal mixers and (mixing) extrusion devices. If mixing is prevented by the melting temperature of the polymer being too high (due to premature peroxide decomposition), the solid state polymer is first provided with epoxide groups by contacting with peroxide; It is recommended that the modified material be melted afterwards. In this way the epoxide groups will be uniformly distributed throughout the matrix. It is also possible to first dissolve the polymer and carry out the reaction with the peroxide in solution.

The practical importance of the present invention is that the point at which the peroxide and polymer are brought into contact with each other and the point at which the peroxide is to be decomposed is independent of other conventional polymer processing steps, such as introduction of additives, molding, etc. This means that you can make a selection.

For example, epoxide groups can first be introduced into the polymer using peroxide, then the additives can be introduced, and the product can then be processed. However, for example,
It is also possible to add peroxide to the polymer together with other additives and decompose the peroxide in a subsequent molding step at elevated temperature, such as an extrusion, compression molding, blow molding or injection molding step. The only restriction here applies to polymers that are ultimately crosslinked. It should be noted that in the case of such polymers, peroxide is in any case present in the polymer before crosslinking.

Examples of suitable polymers that can be modified according to the invention with epoxide groups include saturated polymers such as polyethylene, such as LLDPE, MDPE.

LDPE and HDPE, polypropylene (both isotactic and atactic), ethylene/vinyl acetate copolymer, ethylene/ethyl acrylate copolymer,
Ethylene/methyl acrylate copolymer, ethylene/methyl methacrylate copolymer, chlorinated polyethylene, fluororubber, silicone rubber, polyurethane, polysulfide, polyacrylate rubber, ethylene/propylene copolymer, polyphenylene oxide, nylon,
Polyesters such as polyethylene terephthalate and polybutylene terephthalate, polycarbonates, copolyetheresters, poly(butene-1), poly(butene-2), poly(isobutyne), poly(methylpentene), polyvinyl chloride, polyvinyl chloride/acetic acid Vinyl graft copolymers, polyvinyl chloride/acrylonitrile graft copolymers, and combinations thereof; and unsaturated polymers such as polyptadiene, polyisoprene, poly(cyclopentadiene), poly(methylcyclopentadiene), partially dehydrochlorinated polyvinyl chloride, butadiene/styrene copolymer, acrylonitrile/butadiene/styrene terpolymer, ethylene/propylene/diene monomer terpolymer, isoprene/styrene copolymer, isoprene/isobutylene copolymer, isoprene/styrene/acrylonitrile terpolymer polychloroprene, butadiene/acrylonitrile There are copolymers, natural rubber, and combinations thereof.

Combinations of saturated and unsaturated polymers can also be modified by the present invention. In general, all polymers containing extractable hydrogen atoms can be used in this method.

It has been found that contacting certain polymers with this peroxide causes decomposition of the polymer chains. Its decomposition affects the mechanical properties of the modified polymer. Particularly those polymers that tend to generate tertiary carbon radicals under conditions of peroxide decomposition are susceptible to decomposition. Examples of easily degradable polymers include polyisobutylene, poly(α-
methyl)-styrene, polymethacrylate, polymethacrylamide, polyvinylidene chloride, polypropylene, especially isotactic polypropylene, and polyvinyl alcohol. According to a preferred embodiment of the invention, the inventive modification is carried out in the presence of a coagent. Auxiliaries are generally understood to be customary polyfunctionally reactive additives, such as polysaturated compounds used for crosslinking polymers. This additive will react very quickly with the polymer radicals, overcoming steric hindrance effects and minimizing undesirable side reactions.

Adjuvants (sometimes co-activators)
Rubber Chemistry and Te
Chnology, Volume 61.

pp. 238-254 and W, HOfman, pr.
ogress 1nRubber and Plast
ics Technology, Volume 1, N (12°1
March 1985, pages 18-50 are helpful. . The term "adjuvant" has the same meaning for the present invention.

A wide variety of compounds such as di- and triallyl compounds, di- and triacrylate (and methacrylate) compounds, bismaleimide compounds, divinylbenzene, vinyltoluene, vinylpyridine, valatinone dioxime, 1,2-cis-polyptadiene and their derivatives. Supplements are available. Furthermore, oligomers or polymers of aromatic compounds having at least two alkenyl substituents,
For example, mention should be made of the oligomers of 1,3-diisopropenylbenzene, 1,4-diimpropenylbenzene and 1,3,5-triisopropenyl/benpine. Incorporation of effective amounts of adjuvants into the polymer before or during the reaction with the peroxides avoids deterioration of the mechanical properties and sometimes even results in improvements. Surprisingly, the use of adjuvants increases the adhesion of the resulting modified polymers to supports with greater polarity. This enhanced adhesion can be attributed to the higher efficiency of the introduction of epoxide groups according to the invention when the auxiliary agent is present. However, the present invention is not bound by this theory.

Since the efficiency of the introduction of epoxide groups can be increased in this way, it is considered advantageous to include auxiliaries during the modification reaction even in the modification of polymers that do not undergo significant decomposition. Such polymers, which are generally crosslinked under the action of peroxides, include, for example, polyethylene,
Atactic polypropylene, polystyrene, polyacrylate, polyacrylamide, polyvinyl chloride, polyamide, aliphatic polyester, polyvinylpyrrolidone,
Unsaturated rubbers include polycyclohexane, ethylene propylene rubber, ethylene propylene diene rubber and copolymers thereof. The favorable effects on physical and chemical properties resulting from the presence of epoxide groups, hitherto limited to a relatively small group of polymers, can now be obtained by the present invention also in a large group of other polymers. I can do it. Particularly suitable polymers to be modified by the method of the invention are polyethylene, polypropylene, and ethylene/propylene copolymers, ethylene/vinyl acetate copolymers, ethylene/propylene/diene monomer terpolymers.

The peroxides of this invention generally have 0% by weight based on the weight of the polymer.
．． 01-15% by weight, preferably 0.1-10% by weight,
More preferably it is used in an amount of 1 to 5% by weight. The peroxides of the invention can also be used in combination. The presence of an auxiliary peroxide having a lower decomposition temperature than the peroxide of the present invention may also be advantageous.

The temperature at which the modification is carried out is generally in the range 50° to 350°C, preferably in the range 100° to 250°C.

It should be noted here that in order to obtain optimal results, the duration of the modification step under given conditions should be at least five times the half-life of the peroxide.

As mentioned above, the polymer can further contain conventional additives. Such additives include stabilizers, such as inhibitors against oxidation, thermal and UV degradation, lubricants, extender oils and I'll regulating substances, such as calcium carbonate, mold release agents, colorants, reinforcing or non-toughening. Mention may be made of fillers such as silica, clay, chalk, carbon black and fiber materials, nucleating agents, plasticizers, accelerators, crosslinking agents such as peroxides and sulfur. These additives can be used in conventional amounts.

The invention is further illustrated in the following examples.

Example 1 Preparation of 2-allylperoxy-2-methylpropane (Peroxide 1).

0,1 mol powder KOH being stirred at 5a-10°C
, 35 to a mixture of 0.02 mol of benzyltriethylammonium chloride and 100 ml of methylene chloride.
A mixture of 0.1 mole t-butyl hydroperoxide, 0.1 mole allyl bromide, and 70 ml methylene chloride was added over a period of minutes. After the temperature rose to 20°C, the reaction mixture was stirred at this temperature for 4 hours. After filtration, the methylene chloride solution was concentrated by evaporation under reduced pressure. 60 ml of pentane were added to the residue. The organic phase was washed three times with 15 ml of 10% by weight aqueous potassium hydroxide solution and then with water until pH 7. The organic phase was dried over anhydrous sodium sulfate and concentrated by evaporation under reduced pressure.

7.3 g of a colorless liquid with a peroxide 1 content of 95% determined by G, L, C, were obtained.

Preparation of 3-allylperoxy-3,3-dimethylpropane (peroxide 2).

Peroxide 2 was prepared using the same method described for Peroxide 1. However, 1,1-dimethyl-2-propenyl hydroperoxide was used instead of t-butyl hydroperoxide.

After treatment, 11.0 g of colorless liquid were obtained with a content of peroxide 2 ff 191% determined by G, L, C,.

Preparation of (1-allylperoxy-1-methyl-1-phenyl)ethane (peroxide 3) It was carried out in the same manner as described for oxide 1.

After treatment, 10.3 g of a colorless liquid with a peroxide 3 content of 86% determined by G, L, C, were obtained.

Preparation of 2.5-dimethyl-2,5-di(allylperoxy)hexane (peroxide 4) 0.05 moles of 25-dimethyl-2,5-dihydroperoxyhexane, 1.0 moles of allyl bromide, and 3
Peroxide 4 was prepared in a similar manner to that for peroxide 1 using tetrahydrofuran 5d. After treatment, 8.4 g of a colorless liquid with a peroxide 4 content of 62% determined by G, L, C, were obtained.

Prior to testing the modification, peroxides 1-4 were roughly purified by column chromatography. After treatment, the content of each peroxide was measured by G, L, C,. The structure of each of peroxides 1-4 was confirmed by NMR and IR spectroscopy.

Table 1 shows the peroxide content and half-life of decomposition of 10 hours, 1
time and temperature at 041 hours (0.1 in chloropenpine
M solution) is given for each peroxide.

Preparation of (1-methallylperoxy-1-methyl-1-phenyl)ethane (peroxide 5) 0.11 moles of KOH, 11 moles of water and 0.005 moles of tetraethane are stirred at 10°C. o to a mixture of butylammonium chloride;
io moles of (1-hydroperoxy-1-methyl-1
-phenyl)ethane mixture was added over 30 minutes.

After increasing the temperature to 20° C. over 45 minutes, 25 m of water were added and the organic supernatant phase was separated. 5 to the organic phase
After adding 0I111 petroleum ether (60-80),
Washed twice with 100 ml of water. The organic phase was dried over anhydrous sodium sulfate and concentrated by evaporation under reduced pressure. G
,L,C.

1 with a content of peroxide 5 of 84% determined by
9.0 g of colorless liquid was obtained.

(1-talotylberoxy-1-methyl-1 phenyl)
Preparation of Ethane (Peroxide 6) Peroxide 6 was prepared using the same method as described for peroxide 5, except that crotyl bromide was used in place of t-butyl hydroperoxide.

19.9 g of a pale yellow liquid with a peroxide 6 content of 89% determined by G, L, C, were obtained.

Table a) 1; 2-allylperoxy-2-methylpronogne 2; 3-allylperoxy-3,3-dimethylpropane 3; (1-allylperoxy-1-methyl-1-phenyl)ethane 4; 2.5 -dimethyl-2,5-di(allylperoxy)hexane 5; (1-methallylperoxy-1-methyl-1-phenyl)ethane 6; (1-crotylperoxy-1-methyl-1-phenyl)ethane carried out Example 2 Modification of Polyethylene Using the six peroxides described in Example 1, 50 m of polyethylene (Lupolen 1810H, trademark)
1 Brabender blender at a rotor rotation speed of 30 revolutions/min for 60 minutes. The amount of peroxide and reaction temperature for each experiment are listed in Table 2. In addition, the epoxide content of the obtained polymer is given in the table.

Epoxy content was measured as follows.

Approximately 19 products (weighed to the finest 1 mg) in a 250 ml round bottom flask were weighed at 100 ml under reflux.
m of xylene. After cooling the mixture to 30°C, 4N HC, l! A solution of 1 in 1,4-dioxane of
00d was added after which the mixture was kept at 50°C for 48 hours. Next, add 50 d of acetone, 5 d of water and 5 d of nitric acid with stirring, and then combine the Ag with 0.01 N silver nitrate while stirring.

Titration was carried out by potentiometric titration using an AgCj2 electrode.

Example 3 Modification of renoxide to 2,6-dimethylborif with peroxide 1. The reaction mixture was diluted with monochlorobenzene in a total volume i
oomI! I made it. The treatment time was 6 hours under continuous argon pressure at a temperature of 131°C.

The modified polymer was isolated by adding the reaction mixture to vigorously stirred petroleum ether (60-80) and then filtering the precipitated polymer. The obtained polymer was heated for 17 hours at 70
It was dried under reduced pressure at ℃.

The epoxide content was determined as described in Example 2 and found to be 11.0 mmol epoxy/1007 polymer.

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 120
0ml of hebutane and 2ml of p-)luenesulfonic acid-
Water salt was added and then stirred for 30 minutes at 80°C.

Immediately thereafter, the reaction mixture was dissolved in 2N NaNaOH20
Washed sequentially with O and water until neutral. The organic layer containing heptane and unreacted 1,3-diisopropenylbenzene was evaporated at 100° C. and 1 mbar. 169 g of clear viscous oil were obtained.

Haake Rhcomix with a carrying capacity of 53g of reforming
500™ in an electrically heated mixing chamber, the peroxide prepared in Example 1 and oligo-1,3-diisopropenylbenzene were mixed with polypropylene (Ho
stalen PPLI 0180 P, (commercial a)
, MFI (190°C.

2.16 kg) (6.3 g/10 min, manufactured by Hoechst) were mixed at a temperature of 180° C. for 15 min at a speed of 3 Orpm.

However, the amounts of peroxide and oligo-1,3-diisopropenylbenzene given are calculated based on the weight percent of polypropylene. Torque vs. time during the reaction was recorded on an Iaake Record System 40™, and the 10 minute torque (MIO) was then derived.

The modified polymer was granulated in a Retch™ granulator using a 6m+++ sieve. Fontey
The granulate was pressed between nylon and polyester foil using a
It was molded into a 200 mm plate.

Temperature: 180℃ Without applying pressure 4-8 kPa for 1 minute 41-61 kPa for 1 minute Cooling with water for 3 minutes Tensile strength (TS) and elongation at break (E B) for 9 minutes, Zwi
IS using a ch tensile tester 14.74 (trademark)
Measured according to OS Civil Code 57. Furthermore, a two-component lacquer (2K-PLIRDecklack, manufactured by Akzo Coatings; 2K-Pt1Rl1ardener
, manufactured by Akzo Coatings) according to ASTM
D 429-81. two-component paint,
2K-PUR-11ardcnc+r and 2K-PU
It was manufactured by mixing R-Decklack at a mixing ratio of 3:1 (parts by weight) (pot life 8 hours). The samples were applied by dip coating. The baking conditions were as follows: evaporation separation time (20° C.) for 10 minutes; object temperature 90° C.; time 40 minutes. A specimen measuring 130 mm x 25 mm was used with one end covered with 1 cm adhesive tape, on which the paint was applied as described above.

Dip coated polyamide gaskets were applied and the coatings were dried as described above.

180' peel strength Zwfck tensile tester 1474 2
Measured according to ASTM-D 429-81 using 5 am/min. In addition to indicating the nature of failure, peel strength is expressed as (average peel force)/(diameter of specimen).

In addition, the lap shear force (LSS) is
i-poxy resin (Epikote DX 235™).

Shell) LOg, polyaminoamide (Epilin)
k177, manufactured by Akzo Chemicals) 6g and Silane A
174 (manufactured by Union Carbide) 0.08g
The measurement was carried out using an epoxy resin having the following composition. Plate of polymer modified with resin thin film (40X20X 1m
m) adhesive surface area (20 x 15 mm). Another plate of modified polymer was placed over the adhesive surface area and the two parts were tightly clamped to avoid air occlusion. This construct was kept in a 30° C. stove for 72 hours.

Lap shear forces were measured on a Zwiek tensile testing machine 1474 by measuring the force (kg/cJ) required to pull the plates apart from each other at a rate of 25 mm/min. If the adhesion is broken by shifting the Yuba polymer separately, the measured force is a measure of the adhesion of the epoxy resin. If the polymer breaks before the bond breaks, the force that would cause the bond to break cannot be measured, but it will be greater than the force required to break the polymer. The obtained values are listed in Table 3.

Also listed are the results of comparative experiments conducted in the presence of 1,3-diisopropenylbenzene oligomers.

From the values in Table 3 it is clear that the polypropylene modified in the absence of diisopropenylbenzene is unsuitable for further processing. Modified polypropylene compared to unmodified polypropylene has improved polypropylene's affinity for paints and polymer formulations,
It exhibits improved adhesion, which is very important in the production of composite materials and filled polymers.

Example 5 Adhesion of modified low density polyethylene (LDPE) Example 2
In the method described in the first part of L D P E
(Lupolen 181011. MF [(190
°C; 2.16 kg) 1.3-1.8 g/10 minutes,
BASr) was modified with peroxide 3 and in a separate experiment with peroxide 4.

Each obtained polymer was compressed into a 1 mm thick plate at a temperature of 160° C. for 15 minutes. The peel strength of the two-component lacquer and the lap shear strength (LSS) using epoxy resin were then measured on the delta plates in the manner described in Example 4. Also listed are the results of comparative experiments conducted using unmodified LDPE.

The results clearly show that the adhesion strength obtained using the modified polymer of the present invention is greater than that obtained using unmodified DPE.

table 1) Polymer destruction

Claims (1)

[Claims] 1. A method for modifying a polymer or copolymer using an organic peroxide, the method comprising: contacting the peroxide with the polymer or copolymer and decomposing the peroxide; The above peroxide has a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [In the formula, n is 1, 2 or 3; R^1 is hydrogen, alkyl having 1 to 4 carbon atoms R^2, R^3 and R^4 can be the same or different radicals, and a hydrogen atom or an alkenyl group having 2 to 4 carbon atoms; represents an alkyl group having; 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 may be taken together to form an alkylene group having 3 to 12 carbon atoms, and when n is 1, R is substituted or unsubstituted with a hydroxyl group, t-alkyl group containing 4 to 18 carbon atoms,
p-menth-8-yl, t-alkenyl group containing 5 to 18 carbon atoms, 1-vinylcyclohexyl, or general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (where m is 0, 1 or 2 and R^5 represents an isopropenyl group or a 2-hydroxyisopropenyl group), and when n is 2, R is a group having 8 to 12 groups having a tertiary structure at both ends. Alkylene group with carbon atoms, alkynylene group with 8 to 12 carbon atoms with tertiary structure at both ends, general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X is 0 or 1 and R^5 has the same meaning as above), and when n is 3, R is 1,2,4-triisopropylbenzene-α,α
',α''-tolyl or 1,3,5-triisopropylbenzene-α,α',α''-tolyl]. 2. The method according to claim 1, wherein R^1 is a hydrogen atom or a methyl group. 3. The method of claim 1, wherein R^1, R^2, R^3 and R^4 are hydrogen atoms. 4. The peroxide is 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-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)-1,
1-dimethylpropane, 1-(1-allylperoxy-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- Allylperoxy-1-methylethyl)benzene, 1,3,5-tri(1-allylperoxy-1-methylethyl)benzene, 2,5-di(allylperoxy)-2,5-dimethylhexane, and 2, 5-di(allylperoxy)-2,5-dimethyl-
2. The method of claim 1, wherein the compound is selected from the group consisting of 3-hexyne. 5. The amount of peroxide added is 0.01 to 15% by weight,
5. A method according to any one of claims 1 to 4, characterized in that the reaction temperature is between 50 and 250°C and the duration of the reforming step is at least 5 times the half-life of the peroxide. Method. 6. The method according to claim 5, characterized in that the amount of peroxide added is 0.1-10% by weight and the reaction temperature is 100-200°C. 7. A polymer or copolymer together with an auxiliary agent of the above formula (
Claims 1 to 6 of contacting with the organic peroxide of I)
The method described in any one of the paragraphs. 8. The auxiliary agent is di- and triallyl compounds, di- and triacrylate compounds, di- and trimethacrylate compounds, bismaleimide compounds, divinyl compounds, polyalkenylbenzenes and their polymers, vinyltoluene,
8. The method of claim 7, wherein the compound is selected from the group consisting of vinylpyridine, paraquinone dioxime, polyptadiene, and derivatives thereof. 9. The organic peroxide is used for the modification of polyethylene, polypropylene, copolymers of ethylene and propylene, copolymers of ethylene and vinyl acetate, terpolymers of ethylene, propylene and diene monomers, or 2,6-dimethylpolyphenylene oxide. 8. A method according to any one of claims 1 to 7, characterized in that: 10. The method of any one of claims 1 to 9, wherein the polymer or copolymer is decomposed during the modification. 11. The method of claims 1 to 9, wherein the polymer or copolymer is crosslinked during modification. 12. A molded article produced using the polymer produced by the method of claims 1 to 7. 13. A molded article produced using two or more polymers or copolymers, at least one of which is produced by the method according to any one of claims 1 to 7.