DE2212499B2 - Process for the production of ethylene copolymers and their use for the production of moldings - Google Patents

Description

The tirl bond requires a method of manufacture of ethylene copolymers and their use / for the production of moldings.

From British patent specification 11 46 57 ¹ J it is known to produce binary copolymers of ethylene with glycidylacrylal or glyeidylmelhaerylal with the aid of an iniliator which forms free radicals at temperatures of about 100 to 3 (X) C and pressures of about 700 to 3515 kg / cnr . Investigations have shown that the epoxy ring is opened at higher temperatures in this temperature range, so that there are considerably fewer oxy groups in the resulting copolymer than would correspond to the polymerized glycidyl acrylic or glycidyl methacrylic content. If the polymerization is carried out at lower temperatures in order to avoid the opening of the epoxy ring, the melt index of the resulting copolymers is extremely reduced, so that the film properties of the copolymers are greatly impaired. Furthermore, the polymerization process is unstable.

The object of the invention was to provide Älhyleneopohmcrisate from ethylene, at least one unsaturated monomeric glycidyl compound and optionally at least to create an olefinically unsaturated monomeric compound that has the theoretical content contain on epoxy groups and have advantageous properties, /. B. good displayability. Brittleness at low temperatures, excellent chemical resistance and good compatibility with mil Polyolefins. This task is solved by the solution.

The invention thus relates to a process / ur production of ethylene copolymers by Polymerization of (a) ethylene with Ib) at least one unsaturated monomeric cilycidyl compound and optionally Ie) at least one olelinically unsaturated monomeric compound with the aid of one Free radical initiator at temperatures of 40 to 2 (X) C and pressures of at least 5 (X) kg / cnr in the presence of 0.1 to 4.2 vol- "", alhan, propane, propene, butene-1 or isobutene as Polvmcrisaiionsmodifi / iermillcl. where the Mono-R C O (II, CII

CII,

(J

in the R an oleic unsaturated hydrocarbon residue with I to 20 carbon atoms, unsaturated j-, glycidyl groups of the general formula II

R X CII, CM CII,

O
in the X the group

CH, (J or - O

isl and R hai the foregoing denotation. or l-ipoxyalkcnc of the general formula III

R '
Rc

CH,

(III)

in the R 'a water-loafalom or a methyl group and R has the above meaning.

Specific examples of unsaturated monomeric glycidyl compounds which can be used are glyeidyl acrylate. Glyeidyl methaerylal. Cilycidyl-p-slyrolecarboxylal. Allylglyeidyläthcr, 2-McIlIyIaIIyIgIy! klylülhcr. Slyrolp-Glycidyläthcr (Para-glycid) Islyrole). .1.4-Fpoxy-1-bulcn .M-Fpoxy-.Vmclhyl-1-halide,. \ 4-Fpoxy-1-pcnlen. 3.4-F; poxy-3-methyl-1-phenylene. 5.ft-Fpoxy-l-he \ en and Vinvlevelohcxcnoxid.

Examples of olelinically unsaturated monomeric compounds that can be used are vinyl esters Carboxylic acids with 2 to 5 carbon atoms such as vinyl acetate. Vinyl propionate and vinyl benzene. Acrylic acid esters and methacrylic acid esters of saturated aliphalic cr or cycloaliphatic alcohols with I to IS carbon atoms, such as melhylacryhil, methyl methacrylate. Älhylacrylal. Ethylmelhacrylal. Propyl acrylate. Propylene methacrylal. Bulyl acrylate. Bulylmelh-, iLivIaI. 2-ethylhexyl acrylal. 2-Ä (ethylhexyl methacrylal. Cyclohexyl acrylic. "" yclohcXylmelhacrylal. Dodecyl acrylate. Dodecylmelhacrylal. Ocladecylacrylal and Ocladecvlmclhaerylal. Maleic anhydride. Monoester and Dicsler of malcic acid canhydride with nc-

saturated aliphatic and c> c | t) aliphatic alcohols with I to IH carbon atoms, such as maleic acid monoxide. Maleic acid monoäihj lesler. Maleic acid monohutylsler. Maleic acid monoeyelohcxylesicr. MalcinsäuremonoO-ethylhoxy! Ester ,, Maleic acid monododecyl ester, Maleic acid monoocladecyl ester, maleic acid dimethyl ester, Maleinsüurediülhylesler, Maleic acid dibutyl ester, maleic acid dicyclohexyl ester. Maleic acid - di - 2 - ethylhexylesier. Malcic acid diocladecylsler and malcic acid diocladecylsler. Vinyl chloride. Vinyl ethers such as vinyl methyl ether and vinyl ethyl ether. N-vinyllaciames. like N-vinylpyrrolidone and N-vinyl caprolaclam. Acrylamides, sec-vinyl carbonamides and N-vinyl-N-carhonamides. Particularly preferred monomers are vinyl acetate and the acrylic acid esters.

In the method according to the invention, a polymerization inilialor is used used, the unlcr the polymerization conditions Forms free radicals. These compounds can form oxygen bonds (O () | or contain nitrogen bonds (N = N) in their molecule. Particularly effective inilials are oxygen, Hydrogen peroxide. Peroxides and azo compounds. Particularly preferred polymerization initiators are peroxides and azo compounds of the following general formulas

X -O · - () Y

il
XCOOV

O O

Il Il

XC ^- OOCY

X O C O O Y O O

Il I!

X O C O O C Y

in which X and Y are each hydrogen atoms. lower Alkylrcslc, such as the methyl, alkyl or propyl group. lower alkyl radicals substituted by an aromatic radical. like the Benzyl or Plicniilhy! group, or lower alkyl groups. like clic allyl-. Propenyl or hexenyl group. hcdculcii.

The process according to the invention is carried out at temperatures of about 40 to 200.degree. if the polymerization is carried out at temperatures above 200 C, there is a risk that the epoxy groups subject to a ring opening, so that the content of epoxy groups in the resulting copolymer is decreased. If, on the other hand, the polymerization at temperatures below 4!) C or at Pressures below 500 kg / cm are carried out, isl the rate of polymerization and the conversion greatly reduced, and significantly larger amounts of polymeric ionic ionizer must be used. In addition, low molecular weight products with insufficient elasticity can sometimes be by-products are formed.

The polymerization pressure must be at least about 5 (H) kg / cnr. The upper limit of the pressure depends exclusively on the mechanical wedge of the reaction vessel and the compression used ah.

The amount of polishing modifier used depends on the desired Schmcl / iiulex of the Älhylencopolyrnerisuls to be produced ah. Usually heirägi is the amount of polymerisation.nodi-

Hi lizicrmiüels at least elwa (1.1 percent by volume, based on the total volume of the monomers used. When using less than about 0.1 volume percent shows no significant effect on the increase in the .. Schmcl / iiulex. and it will

ii difficult to apply the polymerization process in Temperature range of about 40 to 2 (X) C to be carried out stably.

For the production of Ethylcncopolymerisal'-n with low Sehmel / index can polymerize in

-Ό Presence of larger amounts of up to 4.2% by volume of the Polymcrisalionsmodificiermitlcls at temperatures of about 40 to 200 C and pressures of at least 5 (K) kg / cnr can be carried out. The copolymer is obtained in high yield. i

_ '■> The Crimping Polymerization Process is carried out in the absence of water and in the absence of inert solvents. Possibly however, an inert solvent can be used as the polymerization medium.

: <i The ethylene copolymer produced in the process If necessary, customary additives such as oxide ion inhibitors can be used. Stabilizers. Antistatic agent. Anti-caking agents or dyes or pigments are incorporated.

: i The Alhylencopolymerisat of the invention draws are characterized by advantageous properties. /. B. Good Vcrarbcitbarkeil. Brittleness at low temperatures and excellent chemical resistance and good compatibility with polyolefins. That

in Älhylencopolynicri.sat of the invention can therefore with the most varied of polyolefins and oil copolymers be mixed to form valuable molding compounds. Furthermore, the Alhyleneopolymcrisal of the invention for the production of reinforced polyolelin

i'i moldings of improved mechanical strength. Dimensional accuracy. Heat resistance and cold resistance can be processed. To this end can the Alhylencopolymcrisal a polyolefin. Fiberglass. Glass powder, (pearls or micro-spheres

"·» Incorporate from glass.

The examples illustrate the invention.

Examples I to 12

Comparative Examples A to 11

A reaction vessel made of corrosion-resistant steel with a capacity is used for the polymerization of 40 liters used, the internal temperature of which can be controlled and the one with an inlet, is provided with an outlet and an agitator. The copolymerization is listed among those in Table I. Conditions carried out, wherein the polymerization initiator is fed continuously.

The results are shown in Table I.

! dragonfly I

(ilwiiKkcil WIlIlIII)! olefinic unsaturated Ethylene I'ulymerisatii in the modifying milie Monomer Name ¹ ) lot Name ¹ 1 lot Surname Menu.· (kghour (kg sid.) Ikg hours) Vol. "." I. (JMA 1.3 200 Λ than 3.1 1 (JMA 2.8 200 propane 1.6 CiMA 1.3 2 (K) Propylene 42 4th CiA 5.5 199 Butene-1 0.5 5 ACJI-: 27.0 2 (M) Isobutene 2.1 6th (JMA 1.3 VA I. 200 Λ ι ha η 3.1 7th (JMA 2.K VA IO 200 propane 1.6 K (JMA 5.5 VA 20th 200 Prop \ len 4.2 y (YES 5.5 MA I. 199 Beware! 0.5 IO ACJI-: 2.7 HA 10 200 Isobr .'Π 2.1 Il f ' \ Λ Λ
VJ JVI. '\ 2.8 VA 0.2 2 (Hi Propyier i.2 12th CiMA t ^ VA 90 2 (M) Propylene 0.2

1 oitsel / unu of Table I.

Poly Poly C. Polymerization initiator merization merization pressure lemperalur. ' Name ¹ ) lot

Polymerization results c

(kg / cm ² )

1,300 1,300 2.6 (M) 1.3 (M) 1.410 1,300 1,300 2,600 1,300 1,410 1,300 1,300

(gStd.i

195 TBHH 15th 195 T Bi-: H 15th 160 CPO 5 180 TBHH Il 190 TBHH 15th 195 TBHH 15th 195 TL-IiI I 15th 160 CPO 5 180 TBHH Il 190 TBHH 15th 195 TBIiH 16 190 TBHII 28

Produce howl

(kgh)

(lewichl * - Ratio \ "Athvlen / u (ihcid} l \ erhiiultini! / ti olefinic

Melting index

■ •.! ■ -Ü-ITIIL'I -'l

93.5: 6.5: 88: 12: 0 91: 9: 0 66: 34: 0 95: 5: 94: 55: 0.5 84: 11: 84: 7: 72:27: I. 83: 12.5: 87 12.9: 0.1 64: 6:

2.0

7.0 20 150

1.2

Il

20th

160

7 60

Opening of the epoxy groups ^a )

(g 10 min) ¹ ) (percent)

4 3 1.5

1.5

1.5

2.5

Continuation of the table

Comparative example

Polymerization conditions cn

Glycidyl compound lot olefinic
Monomer unsaturated Λ ι, ilen Polymeric ion modifiers Name ¹ ) (kgh) Name ¹ ) lot Name amount 1.3 (kg SId.) (kgSld.l Vol,% A. CiMA 2.8 200 B. (.MA 1.3 200 ( (IN THE.. 2 (M) Prnnan 16

Ιοί Isi / l / llll'J

Vn tileic
example

Polymer solution bonds

(ilycidyl entrapment lot olefinic ungcsii
Monomer ittigles Λ ι II Name'l (kg ShIj Niime'l lot 2.X lkg Sid I (kg: <i \ IA 1.3 200 (ΛΙA 2.x VA I. 2 (K) (Al A 1.3 VA IO 2 (H) (iMA 2 pp VA -> 2 (K) CiMA VA ■> 2 (K)

Ion-modified polymer with IcI

Name \ lenee

Vol .- 'o

Propane l.fi

lset / iinLi ilor I a bulk I

Poly- Polymensationsinilialor lot Product Polymerization Results Melt index Opening the mcrisaiions- bulge Epoxy groups ⁴ temperature. C. Name ¹ 1 Weight ratio of Ethylene / u Olycidylvcr- bond to Ig. SIdJ olefinic Ig, IO min) ') (Percent) 13th unsaturated 0.6 32 Il IkgStd.) Monomer I. 0.9 40 220 IBPB 14th 21 94: KkO 1.4 30th 230 TUPB 7th 23.5 89: II: 0 0.01 ^ ·> 220 IBPB 24 94: I ft: 0 (Procedure canceled) IN THE) (PO 13th 14th SS: 12: 0 0.6 32 Il 0.9 40 220 IBPB 14th 21 94: 5.5: 0.5 1.4 30th 230 IBPB 7th 23.5 X5: 10.5: 4.5 0.01> 2 220 TBPB 24 94: 5: I. IW) C PO i 4 82:17: I.

merisalions-

(kg.cm ^; )

1,200
2,500
1,300
1.3 (H)

(Procedure aborted)

Remarks:

¹ I GMA: glycidyl methacrylate; GA: glycidyl acrylic; AGE: allyl glycidyl ether; VA: vinyl acetate; MA: methyl acrylate: EA: ethyl acrylate:

TBEH: tert-butylpeioxy-2-ethylhexanoate; TBPB: tert-butyl peroxybenzoate; CPO: caprylyl peroxide.
^; ) Determined from the elemental analysis, the F.ich curve of the iR-AbsorpiinnsvpckiiuuiN un.J ücrn ürcchi: rg;: r; dci.
Ί Determined by JIS (Japan Industrial Standard) K.-6760.
⁴ ) Determined from the content of unsaturated monomeric glycidyl compound, which was obtained by the ^{method described above under 2} ), and the content of epoxy groups. the by the IR absorption spectrum or according to the hydrochloric acid dimethylformamide

Method has been determined in which the following reactions occur:

CH ul

(1

in I) MI

HCI

CII CH OH Cl

rbcrschult HCI - SaOII

in I) .VII-

NaCl

H, O

It can be seen from the results in Table I that the content of opened epoxy groups can be reduced to a few percent if the poly- «i keeps merization temperature below 200 C. At a temperature above 200 C the proportion is of opened epoxy groups, 30 to 40 percent, even in the presence of a polymerization modifier.

Be i s ρ i el 13 * "

A 260 ml reaction vessel made of corrosion-resistant steel, which is equipped with a stirrer. is flushed with oxygen-free ethylene. Into the reaction vessel. which is held under reduced pressure, 15 mg of caprylyl peroxide, 5.4 g of glycidyl methacrylate, 7 g of vinyl acetate and 0.6 mol of propylene are fed in. Ethylene is then injected into the reaction vessel and the polymerization is carried out with stirring at a temperature of 80 ° C. and a pressure of 1170 kg / cm ^2. After 120 minutes the pressure is reduced to 870 kg / cm ^2. The reaction vessel is cooled, the pressure is relieved and the product is isolated

of an atlivlen- (il \ cid \! melhacr> laI-Viinlacel.il- I erpol \ mcrisats . The product contains Mi (> ewichlsprozcnl C i! vciilvlmclh: icr \ hit and 5 (reu ichlspro / cnt vinyl acetate on (iriiiul der hlementaranalsse and read IR-Absorptionsspeklrum. The (iall on open I po \\ groups, heslimnil according to the hydrochloric acid di met InI f <irma in i <'- M el In is never below 0.5 percent. The polymer has a sehmelzinde \ \ on 1.5.

Example 14

The lines (il \ udylmclhaci> lal Viiiylaeetal-Ί erpohmerisate, in Example 7 and from Veriileiehshe example I are each 15 minutes under one pressure

around KK) kj! cm '.mi at · AliiminiumpliiliL'(I.'D ■ \ M) ■> 0.6 ninil ueprelil and then with a KiihlpiesM. · cooled down. a layer thickness of 1 mm is obtained. The Ahscliälfestiükeit these Schiehlstoffplatten belräi ;! with a deduction angle of 1X0. a temperature of 21) C and a peeling speed of 50 innrin / oku cm or 5.7 kg cm. From this it follows that the (JfI-jiunysurail of the l-po \ idu groups strongly heals the noise of the reports.

liin / \ thylen / (il \ cid \ lmelhaci \ IaI-C opolvmeiisal K ih ctd) ImctliaciA IaI content: 12 (iew iehlprozenl: Schmclzindcv: 2. (11. The analogous to Example 7 has been. hesil / l ciiieAhschalfesiiukeil \ on 7. | k'j cm.

Claims (2)

Patent claims: I. Process / ur production of Λ thy lencopolynierisaien by polymerization of la) ethylene with (b | at least one unsaturated :; monomeric glyeidyl compound and optionally (el at least one further olelinically unsaturated monomeric compound in a weight ratio a: b: c from 5 to ^c J9. ^L J5: 0.05 to 95: 0 to 5 (1 with the help of a free radical initiator at temperatures of 40 to 200 C and pressures of at least 500 kg / cm The presence of 0.1 to 4.2 vol% ethane, propane, propene, 1-butene or isobutene as polymerisation modifier. 2. Use of the gemälf claim 1 hergeslelten Ethyl copolymers / ur production of corporeal bodies. kidneys in a weight ratio a: b: c of 5 to ¹ J _- ¹ J5: 0.05 to ¹ > 5: 0 to 50 per liter. In the process according to the invention, ethylene is used the glyeidyl compound and the oleic unsaturated monomeric compound preferably im C iew ratio from 5 to ')' J, 'J5: 0.1 to 50: 0 to 45 polymerized. As unsaturated monomeric glycidyl compounds those compounds are used that contain an unsaturated child, those with ethylene or copolymerize the olefinically unsaturated monomeric compound. and the at least one F-poxv group contained in the molecule. Preferred examples of unsaturated monomeric glycidyl compounds which can be used are unsaturated glycidyls of the formula I.