U.S. patent application number 08/790342 was filed with the patent office on 2001-08-23 for structural isomers of poly (alkyl ethylenes).
Invention is credited to BUCKA, HARTMUT, BUEHLER, KONRAD, HESSE, ACHIM, PANZER, ULF, RAETZSCH, MANFRED, REICHELT, NORBERT.
Application Number | 20010016628 08/790342 |
Document ID | / |
Family ID | 27215863 |
Filed Date | 2001-08-23 |
United States Patent
Application |
20010016628 |
Kind Code |
A1 |
RAETZSCH, MANFRED ; et
al. |
August 23, 2001 |
STRUCTURAL ISOMERS OF POLY (ALKYL ETHYLENES)
Abstract
Structurally isomeric poly(alkyl ethylenes) with H and Y
structures, polymeric bridging segments and a .PSI. index of
2.times.10.sup.-3 to 8.times.10.sup.-3 (kJ/mole/degree), have
decreased instability in the melt and more advantageous processing
properties. The structurally isomeric poly(alkyl ethylenes) with H
and Y structures are synthesized by an irradiating method, a melt
reaction method or a solid phase reaction method by reacting
poly(alkyl ethylenes) with 0.05 to 5% by weight of monofunctional,
difunctional and polyfunctional monomers, optionally in the
presence of peroxides. The structurally isomeric poly(alkyl
ethylenes) are suitable for producing films, sheets, panels,
coatings, pipes, hollow objects and foams.
Inventors: |
RAETZSCH, MANFRED;
(KIRCHSCHLAG, AT) ; HESSE, ACHIM; (LINZ, AT)
; BUCKA, HARTMUT; (EGGENDORF, AT) ; REICHELT,
NORBERT; (NEUHOFEN, AT) ; PANZER, ULF; (PERG,
AT) ; BUEHLER, KONRAD; (POEDELIST, DE) |
Correspondence
Address: |
JORDAN AND HAMBURG
122 EAST 42ND STREET
NEW YORK
NY
10168
|
Family ID: |
27215863 |
Appl. No.: |
08/790342 |
Filed: |
January 27, 1997 |
Current U.S.
Class: |
525/263 ;
525/307; 525/311; 525/313; 525/319 |
Current CPC
Class: |
C08F 210/08 20130101;
C08F 8/00 20130101; C08F 210/16 20130101; C08F 210/08 20130101;
C08F 210/14 20130101; C08F 210/08 20130101; C08F 210/06 20130101;
C08L 2666/04 20130101; C08F 212/08 20130101; C08F 210/08 20130101;
C08F 210/14 20130101; C08F 110/08 20130101; C08F 210/00 20130101;
C08F 210/16 20130101; C08F 210/16 20130101; C08F 110/10 20130101;
C08F 110/06 20130101; C08F 210/06 20130101; C08F 210/00 20130101;
C08F 210/06 20130101; C08F 8/00 20130101; C08F 210/08 20130101;
C08F 210/16 20130101; C08F 8/48 20130101; C08L 23/04 20130101; C08L
23/04 20130101 |
Class at
Publication: |
525/263 ;
525/307; 525/311; 525/313; 525/319 |
International
Class: |
C08F 255/00; C08F
265/00; C08F 265/04 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 1, 1996 |
DE |
196 03600.3-44 |
Feb 1, 1996 |
DE |
196 03439.6-44 |
Feb 1, 1996 |
DE |
196 03438.8-44 |
Claims
1. Structurally isomeric poly(alkyl ethylenes) having improved
processability and a melt of lower instability, characterized in
that the poly(alkyl ethylenes) have H and Y structures and a .PSI.
index of 2.times.10.sup.-3 to 8.times.10.sup.-3 (kJ/mole/degree),
.PSI. being defined as below
.PSI.=Tm.times..DELTA.Hm.times..beta..times..xi..times.T- g.sup.-1
(kJ/mole/degree) in which Tm=melting temperature (.degree. K)
.DELTA.Hm=heat of fusion (kJ/mole) .beta.=coefficient of linear
thermal expansion at 25.degree. C. (1/degree) .xi.=threshold value
(strand diameter of structurally isomeric poly(alkyl
ethylene/strand diameter of unmodified poly(alkyl ethylene) when
determining the MFI by the method of ISO 1131 Tg=glass transition
temperature (.degree. K), are poly(alkyl ethylenes) with
H-structure macromers of the structure wherein R.sub.1.dbd.C.sub.1
to C.sub.4 alkyl, R.sub.2.dbd.H, t/u=0.03 to 30,
R.sub.3.dbd.C.sub.1 to C.sub.4 alkyl or H, R.sub.4.dbd.H, C.sub.1
to C.sub.4 alkyl, halogen or aryl, particularly phenyl, R.sub.5
.dbd.H or C.sub.1 to C.sub.4 alkyl and y+z =150 to 3,000.
=polymeric bridging segments based on acrylic acid, C.sub.4 to
C.sub.12 acrylic acid derivatives, C.sub.3 to C.sub.2, allyl
compounds, C.sub.8 to C.sub.14 diacrylates, C.sub.7 to C.sub.16
diallyl compounds, C.sub.4 to C.sub.10 dienes, C.sub.9 to C.sub.15
dimethacrylates, C.sub.7 to Clo divinyl compounds, C.sub.3 to
C.sub.16 monovinyl compounds, C.sub.12 to C.sub.17 polyacrylates,
C.sub.15 to C.sub.21 polymethacrylates, and/or C.sub.9 to C.sub.12
triallyl compounds and poly(alkyl ethylenes) with a Y structure are
macromers having the structure in which R.sub.1.dbd.C.sub.1 to
C.sub.4 alkyl, R.sub.2.dbd.H, R.sub.3.dbd.C.sub.1 to C.sub.4 alkyl,
halogen or aryl, particularly phenyl, R.sub.5.dbd.H or C.sub.1 to
C.sub.4 alkyl, y+z=150 to 3,000, t/u=0.03 to 30 and w=250 to 5,000
=polymeric bridging segments based on acrylic acid, C.sub.4 to
C.sub.12 acrylic acid derivatives, C.sub.3 to C.sub.21 allyl
compounds, C.sub.8 to C.sub.14 diacrylates, C.sub.7 to C.sub.16
diallyl compounds, C.sub.4 to C.sub.10 dienes, C.sub.9 to C.sub.15
dimethacrylates, C.sub.7 to C.sub.10 divinyl compounds, C.sub.3 to
C.sub.16 monovinyl compounds, C.sub.12 to C.sub.17 polyacrylates,
C.sub.15 to C.sub.21 polymethacrylates, and/or C.sub.9 to C.sub.12
triallyl compounds, wherein the proportion of polymeric bridging
elements in the poly(alkyl ethylenes) with H and Y structures is
0.1 to 5% by weight.
2. The structurally isomeric poly(alkyl ethylenes) of claim 1,
characterized in that the structurally isomeric polyalkylethylenes
are defined by the following structural combinations of the
substituents R.sub.1 to R.sub.5: a)
R.sub.1.dbd.R.sub.3.dbd.R.sub.4.dbd.C.sub.2H.sub.5 and
R.sub.2.dbd.R.sub.5.dbd.H b)
R.sub.1.dbd.R.sub.3.dbd.C.sub.2H.sub.5,
R.sub.2.dbd.R.dbd.R.sub.5.dbd.Hand t/u=1.2 to 32 c)
R.sub.1.dbd.R.sub.3.dbd.R.sub.4.dbd.i-C.sub.4H.sub.9 and
R.sub.2.dbd.R.sub.5.dbd.H d)
R.sub.1.dbd.R.sub.3.dbd.i-C.sub.4H.sub.9,
R.sub.2.dbd.R.sub.4.dbd.R.sub.5.dbd.H and t/u=1.2to 32 e)
R.sub.1.dbd.R.sub.3.dbd.i-C.sub.4H.sub.9,
R.sub.2.dbd.R.sub.5.dbd.H, R.sub.4.dbd.n-C.sub.4H.sub.9 and
t/u=0.03to 3 f) R.sub.1.dbd.R.sub.3.dbd.- R.sub.4.dbd.CH.sub.3and
R.sub.2.dbd.R.sub.5.dbd.H g) R.sub.1.dbd.R.sub.3.dbd.CH.sub.3,
R.sub.2.dbd.R.sub.4.dbd.R.sub.5.dbd.H and t/u=1.2to32 h)
R.sub.1.dbd.R.sub.3.dbd.CH.sub.3, R.sub.2.dbd.R.sub.5.dbd.H,
R.sub.4.dbd.Cl and t/u=0.03 to 5
3. The structurally isomeric poly(alkyl ethylenes) of claims 1 and
2, characterized in that the poly(alkyl ethylenes) with H and Y
structures are mixtures of the structurally isomeric poly(alkyl
ethylenes) of claim 2.
4. The structurally isomeric poly(alkyl ethylenes) of claims 1 to
3, characterized in that the .PSI. index is 2.5.times.10.sup.-3 to
6.times.10.sup.-3 (kJ/mole/degree).
5. The structurally isomeric poly(alkyl ethylenes) of claims 1 to
4, characterized in that the polymeric bridging compounds comprise
sequences with monomeric units of monovinyl compounds in amounts of
1.5 to 5% by weight, sequences with monomeric units of divinyl
compounds in amounts of 0.1 to 2% by weight, sequences with
monomeric units of allyl compounds in amounts of 0.2 to 4.5% by
weight, sequences with monomeric units of diacrylates in amounts of
0.1 to 1.6% by weight, sequences with monomeric units of
polyacrylates in amounts of 0.1 to 1.2% by weight, sequences with
monomeric units of acrylic acid and/or derivatives of acrylic acid
in amounts of 0.2 to 1.8% by weight, sequences with monomeric units
of diallyl compounds in amounts of 0.2 to 1.8% by weight, sequences
with monomeric units of dimethacryl ates in amounts of 0.1 to 1.6%
by weight, sequences with monomeric units of dienes in amounts of
0.1 to 1.6% by weight, sequences with monomeric units of
polymethacrylates in amounts of 0.1 to 1.2% by weight and/or
sequences with monomeric units of triallyl compounds in amounts of
0.1 to 1.4% by weight.
6. Mixtures of poly(alkyl ethylenes), characterized in that the
mixtures comprise 3 to 97% poly(alkyl ethylenes) with the H and Y
structures of claims 1 to 5, 97 to 3% of unmodified poly(alkyl
ethylenes), 0.5 to 45% of conventional auxiliary materials,
particularly of 0.01% to 0.6% by weight of phenolic antioxidants,
0.01% to 0.6% by weight of high-temperature stabilizers based on
disulfides and thioethers, 0.01 to 0.6% of processing stabilizers
based on phosphites and/or 0.01% to 0.8% of sterically hindered
amines (HALS) and, optionally, 0.1% to 1% of antistatic agents,
0.2% to 3% of pigments, 0.05% to 1% of nucleating agents, 5% to 40%
of fillers, 2% to 20% of flame retardants and/or 0.001% to 1% of
processing aids, and have a .PSI. index from 2.times.10.sup.-3 to
7.8.times.10.sup.-3 (kJ/mole/degree).
7. A method of synthesizing structurally isomeric poly(alkyl
ethylenes) of claims 1 to 6, characterized in that poly(Cl to
C.sub.4-alkyl ethylenes), preferably under continuous processing
conditions in a first step of the reaction are subjected as powdery
mixtures with 0.02 to 5% by weight of acrylic acid, acrylic acid
derivatives, allyl compounds, diacrylates, diallyl compounds,
dienes, dimethacrylates, divinyl compounds, monovinyl compounds,
polyacrylates, polymethacrylates and/or triallyl compounds in a
fluidized bed, preferably under inert conditions, at 300.degree. to
500.degree. K, optionally in the presence of additional,
conventional auxiliary materials, particularly of 0.01 to 0.6% by
weight of phenolic antioxidants, 0.01 to 0.6% by weight of
high-temperature stabilizers based on disulfides and polyethers,
0.01 to 0.6% of processing stabilizers based on phosphites and/or
0.01 to 8% sterically hindered amines (HALS), 0.1 to 1% of
antistatic agents, 0.2 to 3% of pigments, 0.05 to 1% of nucleating
agents, 5 to 40% of fillers, 2 to 20% of flame retardants and/or
0.001 to 1% of processing aids, preferably in fluidized bed
reactors with continuous feeding and discharging of product, to
ionizing radiation having an energy of 150 to 10,000 KeV at a
radiation dose of 0.5 to 80% KGy, particularly by means of nuclide
irradiating equipment with cobalt 60 as radiation sources, by means
of electron beam accelerators of the Cockroft-Walton type with
radiation energies of 300 to 4500 KeV or by means of electron beam
accelerators of the linear accelerator type with beam current
energies of 1,000 to 10,000 KeV, and in a second step of the
reaction, the irradiated, powdery mixtures are treated thermally at
380.degree. to 550.degree. K, particularly in extruders at
temperatures ranging from 410.degree. to 550.degree. K and at
reaction times of 2 to 10 minutes or in the solid phase at
temperatures ranging from 380.degree. to 500.degree. K at reaction
times from 5 to 60 minutes, it being possible to add, in addition,
conventional stabilizers in concentrations of 0.01% to 0.6% before
the thermal treatment.
8. A method of synthesizing structurally isomeric poly(alkyl
ethylenes) of claims 1 to 6, characterized in that poly(Cl to
C.sub.4-alkylethylenes), in the melt in the extruder, preferably
under inert conditions are reacted in a first step of the reaction
with 0.01% to 3% by weight of acyl peroxides, alkyl peroxides,
hydroperoxides and/or peresters, which are either drummed up on the
poly(alkyl ethylenes) in the kneader and metered together or
metered as a solution into the poly(alkyl ethylene) melt in zones 2
to 4 of the extruder, and in a second step of the reaction, are
caused to react with 0 01% to 5% by weight of acrylic acid or
acrylic acid derivatives, allyl compounds, diacrylates, diallyl
compounds, dienes, dimethacrylates, divinyl compounds, monovinyl
compounds, polyacrylates, polymethacrylates and/or triallyl
compounds, in the presence of 0.001% to 3.0% by weight of acyl
peroxides, alkyl peroxides, hydroperoxides and/or peresters, and
optionally conventional auxiliaries, particularly 0.01 to 0.6% by
weight of phenolic antioxidants, 0.01% to 0.6% by weight of
high-temperature stabilizers based on disulfides and polyethers,
0.01% to 0.6% of processing stabilizers based on phosphites and/or
0.01% to 0.8% of sterically hindered amines (HALS), 0.1% to 1% of
antistatic agents, 0.2% to 3% of pigments, 0.05% to 1% of
nucleating agents, 5% to 40% of fillers, 2 to 20% of flame
retardants and/or 0.001% to 1% of processing aids at temperatures
of 140.degree. to 320.degree. C., the radical-forming agents and
the monomers being metered in over separate metering equipment
and/or jointly as a solution into the poly(alkyl ethylene) melt in
zones 3 to 6 of the extruder, optionally with a further portion of
poly(alkyl ethylene).
9. A method of synthesizing structurally isomeric poly(alkyl
ethylenes) of claims 1 to 6, characterized in that poly(C.sub.1 to
C.sub.4-alkylethylenes), preferably under continuous processing
inert conditions, are subjected in the first step of the method at
290.degree. to 500.degree. K in reactors with rotating equipment
and circulating carrier gas, to a sorption with 0.05% to 3% acyl
peroxides, alkyl peroxides, hydroperoxides and/or peresters, as
well as with 0.05% to 5% by weight of acrylic acid, acrylic acid
derivatives, allyl compounds, diacrylates, diallyl compounds,
dienes, dimethacrylates, divinyl compounds, monovinyl compounds,
polyacrylates, polymethacrylates and/or triallyl compounds, which
were introduced over vaporizing equipment into the carrier-gas
stream, and the powdery mixtures, in a second step of the method,
optionally with the addition of conventional auxiliary materials,
particularly of 0.01% to 2.5% of stabilizers, 0.1% to 1% of
antistatic agents, 0.2% to 3% of pigments, 0.05% to 1% of
nucleating agents, 5% to 40% of fillers, 2% to 20% of flame
retardants and/or 0.001% to 1% of processing aids, are heated in
the feed zone of the screw injection molding machine, particularly
double-screw extruders or single-screw extruders with plunger
screw, to the decomposition temperature of the radical-forming
agent and subsequently melted at reaction temperatures of
415.degree. to 596.degree. K and granulated.
10. A method for the synthesis of structurally isomeric poly(alkyl
ethylenes) of claims 1 to 9, characterized in that, as poly(alkyl
ethylenes), poly(ethyl ethylenes) with glass transition
temperatures of 242.degree. to 250.degree. K and molecular weights
(M.sub.w) ranging from 2.times.10.sup.4 to 3.times.10.sup.6,
poly(ethyl ethylene co-ethylene) copolymers, containing 3 to 45
mole percent ethylene in the copolymer, poly(ethyl ethylene
co-methylethylene) copolymers, containing 3 to 97 mole percent of
methylethylene in the copolymer, poly(isobutylenes) with glass
transition temperatures of 295.degree. to 303.degree. K and
densities ranging from 0.813 to 0.832 g/cc at 25.degree. C.,
poly(isobutyl ethylene co-n-butylethylene) copolymers with an
n-butylethylene content of 3 to 97 mole percent, poly(isobutyl
ethylene co-ethylene) copolymers with an ethylene content in the
copolymer of 3 to 45 mole percent, poly(methyl ethylenes) with
glass transition temperatures ranging from 259.degree. to
266.degree. K and molecular weights (M.sub.w) ranging from
1.times.10.sup.5 to 8.times.10.sup.5 and/or poly(methyl ethylene
co-ethylene) copolymers with an ethylene content in the copolymer
of 3 to 45 mole percent, are used.
11. The use of structurally isomeric poly(alkyl ethylenes) of
claims 1 to 5, as well as of the mixtures of claim 6, for the
production of films, sheets, panels, coatings, pipes, hollow
objects and foams.
Description
[0001] In contrast to polyethylene, poly(alkyl ethylenes) have a
series of disadvantages for thermoplastic processing, such as an
increased instability of the melt and, associated therewith, a
smaller processing window. Compared to polyethylene, unmodified
poly(alkyl ethylenes) can be processed only at a significantly
lower rate.
[0002] Poly(ethyl ethylenes) of improved processability are
attained by the synthesis of poly(ethyl ethylene co-ethylene)
copolymers (Natta, G., J. Polymer Sci. 51 (1961), 387 - 398; Chim.
Ind. (Milano) 41 (1959), 764; Yu, T., J. Plastic Film Sheeting 10
(1994) 1, 539 - 564), as well as by grafting with styrene, vinyl
chloride (Natta, Polymer Sci. 34 (1959), 685 - 698) or
acrylonitrile (U.S. Pat. No. 3,141,862). Blends of poly(ethyl
ethylene) and polyethylene likewise have favorable processing
properties (Hwo, C., J. Plast. Film Sheeting 3 (1987), 245 - 260;
Kishore, K., Polymer 27 (1986), 337 - 343).
[0003] It is furthermore known that the instability of poly(methyl
ethylene) melts can be decreased by additions of polyethylene
(Ramsteiner, F., Polymer 24 (1983), 365 - 370),
polyethylene/poly(ethylen- e co-methylethylene) mixtures (Wasiak,
A., ANTEC 1992, 1265 - 1266) or poly(ethylene co-acetoxyethylene)
(Gupta, A. J. Appl. Polymer. Sci. 46 (1992), 281 - 293). Enlarging
the processing window of poly(methyl ethylene) is also brought
about by treating the powder in the solid phase with ionizing
radiation (EP 190889), peroxides (EP 384431) or monomer/peroxide
mixtures (EP 437808). A treatment of poly(methyl
ethylene)/polyethylene melts with peroxides is also known (Xanthos,
M., Adv. Polym. Techn. 11 (1992) 4, 295 - 304).
[0004] Known methods for decreasing the melt instability of
poly(isobutyl ethylene) are the synthesis of poly(isobutyl ethylene
co-ethylene) copolymers (Yu, T., J. Plast. Film Sheeting 10 (1994)
1, 539 - 564), poly(isobutyl ethylene co-hexyl ethylene) copolymers
and poly(isobutyl ethylene co-hexadecylethylene) copolymers
(Campbell, J. Appl. Polymer Sci. 5 (1961) 4, 184 - 190, Hambling,
J., Rubber Plast. Age 49 (1968) 3, 224 - 227), of poly(isobutyl
ethylene co-phenylethylene) copolymers (Krenzel, V., Plast. Massy
(1972) 3, 57 - 59; Kissin, Y., Eur. Polymer J. 8 (1972) 3, 487 -
499) as well as the synthesis of poly(isobutyl ethylene
g-phenylethylene) graft copolymer (Wilson, J., J. Macromol. Sci. A6
(1972) 2, 391 - 402).
[0005] Also known is the cross linking of poly(methyl ethylene
co-ethylene), poly(methyl ethylene) and poly(acetyl ethylene
co-ethylene) by irradiation to increase the thermoforming stability
and the modulus (N. Brooks, J. Irradiation Techn. 1 (1983)3, 237 -
257). Furthermore, investigations have been made of the absorption
of monomers by powdery poly(alkyl ethylenes) (Rtzsch, M., Angew.
Makromol. Chemie 229 (1995), 145 - 158).
[0006] It is a disadvantage of these methods that the advantageous
material properties of poly(alkyl ethylenes), such as thermoforming
stability, transparency and modulus, are decreased by the high
proportion of modifying components during the copolymerization,
grafting and alloying.
[0007] The invention is therefore based on the problem of improving
the processing properties of poly(alkyl ethylenes), so as to obtain
the latter with advantageous material properties. This problem was
surprisingly solved by the structural isomerization of poly(alkyl
ethylenes) for which poly(alkyl ethylenes) of different chain
length are linked by polymeric bridging segments into structurally
isomeric poly(alkyl ethylenes) with an H and a Y structure.
[0008] The .PSI. index has proven to be a suitable criterion for
characterizing the processing behavior of poly(alkyl
ethylenes):
.PSI.=Tm.times..DELTA.Hm.times..beta..times..xi..times.Tg.sup.-1
(kJ/mole/degree)
[0009] in which
[0010] Tm=melting temperature (.degree. K)
[0011] .DELTA.Hm=heat of fusion (kJ/mole)
[0012] .beta.=coefficient of linear thermal expansion at 25.degree.
C. (1/degree)
[0013] .xi.=threshold value
[0014] Tg=glass transition temperature (.degree. K)
[0015] The melting temperature (Tm(.degree. K) and heat of fusion
.DELTA.Hm (kJ/mole) are determined according to the methods of the
DIN 51004 or ISO 3146. The coefficient of linear thermal expansion
.beta. (1/degree) at 24.degree. C. is determined according to the
method of DIN 53752. The threshold value .xi. is determined by the
MFI determination according to the method of the ISO 1131 by
determining the strand diameter of the structurally isomeric
polyalkyl ethylene d.sub.I (mm) produced, as well as the strand
diameter of the unmodified polyalkylethylene starting material
d.sub.A (mm) and forming the ratio d.sub.I/d.sub.A. The glass
transition temperature is determined by the method of DIN
61006.
[0016] For the starting materials (unmodified polyalkylethylene),
the melting temperature, glass transition temperature, heat of
fusion and coefficient of linear thermal expansion .beta. can be
taken from tabulated values, such as those of Brandrup-Immergut
"Polymer Handbook", John Wiley & Sons, New York, 1989 (ISBN
0-471-81244-7).
[0017] Pursuant to the invention, the poly(alkyl ethylenes), with
an H and a Y structure and a .PSI. index of 2.times.10.sup.-3 to
8.times.10.sup.-3 (kJ/mole/degree), have significantly more
advantageous processing properties than do unmodified poly(alkyl
ethylenes). For example the .PSI. value is of the order of
1.88.times.10.sup.-3 (kJ/mole/degree) for poly(isobutyl ether) and
1.84.times.10.sup.-3 (kJ/mole/degree) for poly (ethyl
ethylene),
[0018] Poly(alkyl ethylenes) with an H structure are macromers of
the structure 1
[0019] wherein
[0020] R.sub.1.dbd.C.sub.1 to C.sub.4 alkyl, R.sub.2.dbd.H,
t/u.dbd.0.03 to 30, R.sub.3=C.sub.1 to C.sub.4 alkyl or H,
R.sub.4.dbd.H, C.sub.1 to C.sub.4 alkyl, halogen or aryl,
particularly phenyl, R.sub.5.dbd.H or C.sub.1 to C.sub.4 alkyl and
y+z=150 to 3,000.
[0021] =polymeric bridging segments based on acrylic acid, C.sub.4
to C.sub.12 acrylic acid derivatives, C.sub.3 to C.sub.21 allyl
compounds, C.sub.8 to C.sub.14 diacrylates, C.sub.7 to C.sub.16
diallyl compounds, C.sub.4 to C.sub.10 dienes, C.sub.9 to C.sub.15
dimethacrylates, C.sub.7 to C.sub.10 divinyl compounds, C.sub.3 to
C.sub.16 monovinyl compounds, C.sub.12 to C.sub.17 polyacrylates,
C.sub.15 to C.sub.21 polymethacrylates, C.sub.9 to C.sub.12
triallyl compounds and/or macromers based on oligobutadienes,
polysiloxanes and/or polyethers.
[0022] Poly(alkyl ethylenes) with a Y structure are macromers
having the structure 2
[0023] in which R.sub.1.dbd.C.sub.1 to C.sub.4 alkyl,
R.sub.2.dbd.H, R.sub.3.dbd.C.sub.1 to C.sub.4 alkyl or H,
R.sub.4.dbd.H, C.sub.1 to C.sub.4 alkyl, halogen or aryl,
particularly phenyl, R.sub.5.dbd.H or C.sub.1 to C.sub.4 alkyl,
y+z=150 to 3,000, t/u=0.03 to 30 and w=250 to 5,000.
[0024] =polymeric bridging segments based on acrylic acid, C.sub.4
to C.sub.12 acrylic acid derivatives, C.sub.3 to C.sub.2, allyl
compounds, C.sub.8 to C.sub.14 diacrylates, C.sub.7 to C.sub.16
diallyl compounds, C.sub.4 to C.sub.10 dienes, C.sub.9 to C.sub.15
dimethacrylates, C.sub.7 to C.sub.10 divinyl compounds, C.sub.3 to
C.sub.16 monovinyl compounds, C.sub.12 to C.sub.17 polyacrylates,
C.sub.15 to C.sub.21 polymethacrylates, C.sub.9 to C.sub.12
triallyl compounds and/or macromers based on oligobutadienes,
polysiloxanes and/or polyethers.
[0025] The proportion of polymeric bridging elements in the
poly(alkyl ethylenes) with H and Y structures is 0.1 to 5% by
weight.
[0026] Due to the structural isomerization of poly(alkyl ethylenes)
to structurally isomeric poly(alkyl ethers) with H and Y
structures, a chain arrangement, which greatly decreases the melt
instability of the poly(alkyl ethylenes), is achieved in the
melt.
[0027] Poly(alkyl ethylenes) with an H and a Y structure are
preferred, in which R.sub.1 and R.sub.3 are formed by ethyl, methyl
or isobutyl groups, R.sub.2 and R.sub.5 are formed by H and R.sub.4
is formed by ethyl, n-butyl, methyl or isobutyl groups or by H or
Cl.
[0028] Mixtures of these structurally isomeric poly(alkyl
ethylenes) also have these inventive properties. Preferred .PSI.
values lie between 2.5.times.10.sup.-3 and 6.times.10.sup.-3
(kJ/mole/degree).
[0029] Suitable monovinyl compounds for the bridging segments are
p-acetoxystyrene, aminostyrene, t-butylstyrene, bromostyrene,
chlorostyrene, dichlorostyrene, m-diethylaminoethylstyrene,
diethylene glycol monovinyl ether, dimethoxystyrene,
dimethylstyrene, ethoxystyrene, ethylstyrene, ethyl vinyl acetate,
ethyl vinyl ether, ethylvinylpyridine, fluorostyrene,
2-hydroxybutylstyrene, 2-hydroxypropylstyrene, m-hydroxystyrene,
isopropylstyrene, methoxystyrene, methyl-chlorostyrene,
.alpha.-methylstyrene, m-methylstyrene, p-methylstyrene, methyl
vinyl acetate, methyl vinyl ether, methylvinylpyridine,
4-phenoxystyrene, phenyl vinyl ether, styrene, trimethoxystyrene,
trimethylstyrene, vinyl acetate, vinyl acetoxy methyl ketone, vinyl
adipate, 9-vinyl anthracene, vinyl benzoate, vinyl butyl ether,
vinyl butyl ketone, vinyl butyrate, vinyl carbazole, vinyl
cyanoacetate, vinyl dodecyl ether, vinyl ether,
vinylethyldiethoxysilane, vinyl ethyl ether, vinyl ethylene glycol
glycidyl ether, vinyl ethylhexyl ether, vinyl ethyl ketone, vinyl
forrnate, vinylfuran, vinyl hexyl ether. vinylimidazole, vinyl
isobutyl ether, vinyl isocyanate, vinyl isopropyl ether, vinyl
isopropyl ketone, vinyl laurate, vinylmethyldiacetoxysilane,
vinylmethyldiethoxysilane, vinyl methyl ether, vinyl methyl ketone,
vinylnaphthalene, vinyl octadecyl ether. vinyl octyl ether,
N-vinyloxazolidone, vinyl pelargonate, o-vinylphenol,
vinylphenyldimethylsilane, vinyl phenyl ether, vinyl phenyl ketone,
5-vinylpicoline, vinyl propionate, N-vinylpyridine,
N-vinylpyrrolidone, vinyl stearate, vinyltriethoxysilane,
vinyltrimethoxysilane, vinyl-tris(trimethoxysiloxy)- silane and/or
vinyltrimethylsilane in amounts of 1.5% to 5% by weight.
[0030] Suitable as divinyl compounds for the polymeric bridging
segments are divinylaniline, m-divinylbenzene, p-divinylbenzene,
diethylene glycol divinyl ether, divinylpentane, divinylpropane
and/or 1,3-divinyl-1,1,3,3-tetramethyldisiloxane in amounts of 0.1%
to 2% by weight.
[0031] Polymeric bridging segments based on allyl compounds
comprise monomeric units such as allyl acetate, allyl acrylate,
allyl alcohol, allylbenzene, allyl benzyl ether, 3-allyl-1-butene,
allyl butyl ether, allyl cyanurate, allylcyclohexane, allyl diethyl
ketone, 4-allyl-2,6-dimethoxyphenol, allyldimethylchlorosilane,
allyl epoxy propyl ether, allyl ethyl ether, allyl glycidyl ether,
allyl glycidyl hexyl hydrophthalate, allyl glycidyl phthalate,
allyl heptanoate, allyl hexanoate, allyl methacrylate,
allylmethoxyphenol, allyl methyl ether, allyl methyl maleate,
allyloxy-2,3-propylene glycol, N-allyl stearamide, allyl tolyl
ether, allyltrichlorosilane, allyltriethoxysilane,
allyltrimethoxysilane, allyltrimethylsilane, allyltriphenylsilane
and/or allyl vinyl ether in amounts of 0.2% to 4.5% by weight,
based on the inventive poly(alkyl ethylenes) with H and Y
structures.
[0032] Diacrylates or dimethacrylates suitable for the polymeric
bridging segments are ethylene glycol diacrylate, propylene glycol
diacrylate, trimethylene glycol diacrylate, butylene glycol
diacrylate, dihydroxypentane diacrylate, dihydroxyhexane
diacrylate, dihydroxyoctane diacrylate, diglycol diacrylate and/or
triglycol diacrylate and dimethacrylates such as ethylene glycol
dimethacrylate, propylene glycol dimethacrylate, trimethylene
glycol dimethacrylate, butylene glycol dimethacrylate,
dihydroxypentane dimethacrylate, dihydroxyhexane dimethacrylate,
dihydroxyoctane dimethacrylate, diglycol dimethacrylate and/or
triglycol dimethacrylate in amounts of 0.1% to 1.6% by weight.
[0033] Glycerin triacrylate, trimethylolpropane triacrylate and/or
pentaerythritol tetraacrylate, in amounts of 0.1% to 1.2% by
weight, are suitable as polyacrylates for the polymeric bridging
segments . Aside from polymeric bridging segments based on acrylic
acid, polymeric bridging segments preferably have acrylic acid
derivatives, such as acrylamide, acrylonitrile, benzyl acrylate,
butyl acrylate, cyclohexyl acrylate, N,N-dimethylacrylamide,
dodecyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate,
2-ethoxyethyl acrylate, glycidyl acrylate, hydroxyethyl acrylate,
isopropyl acrylate, 2-methoxyethyl acrylate, 4-methoxybenzyl
acrylate, methyl acrylate, sodium acrylate,
N-t-butoxycarbonyl-2-aminoethyl acrylate, octyl acrylate,
phenylmethyl acrylate, phenyl acrylate, n-propyl acrylate and/or
tetrahydrofurfuryl acrylate, in amounts of 0.2% to 1.8% by weight,
based on the inventive poly(alkyl ethylenes) with H and Y
structures.
[0034] As diallyl compounds for the polymeric bridging segments ,
diallyldimethylsilane, diallyl(2-hydroxy-3-phenoxypropyl)
isocyanurate, diallyl cyanurate, diallylcyanoethyl isocyanurate,
diallyl cyanamide, diallyl maleate, diallylmelamine, diallyl
phthalate and/or N,N' diamide of diallyltartaric acid in amounts of
0.2% to 1.8% by weight are suitable.
[0035] Polymeric bridging segments based on dienes consist of
monomeric units, such as butadiene, butadiene-1-carboxylic acid,
chloroprene, 1.3-cyclohexadiene, 1,5-cyclohexadiene,
cyclopentadiene, 2,3-dimethylbutadiene, 1-ethoxybutadiene,
1,4-heptadiene, 1,4-hexadiene, 1,6-hexadiene, isoprene,
norbornadiene and/or 1,4-pentadiene in amounts of 0.1% to 1.6% by
weight, based on the inventive poly(alkyl ethylenes) with H and Y
structures.
[0036] Preferred polymeric bridging segments , based on
polymethacrylates consist of monomeric units such as glycerin
trimethacrylate, trimethylolpropane trimethacrylate and/or
pentaerythritol methacrylate in amounts of 0.1% to 1.2% by
weight.
[0037] As triallyl compounds for polymeric bridging segments ,
triallyl citrate, triallyl cyanurate, triallyl isocyanurate and/or
triallyl phosphine, in amounts of 0.1% to 1.4% by weight, are
suitable.
[0038] Suitable macromers for polymeric bridging segments are based
on oligobutadienes, polysiloxanes and/or polyethers with terminal
acrylic, allyl, isocyanate, oxazoline or vinyl groups, in amounts
of 0.8% to 5% by weight, based on the inventive poly(alkyl
ethylenes) with H and Y structures.
[0039] Pursuant to the invention, mixtures of 3% to 97% of
poly(alkyl ethylenes) with H and Y structures, 97% to 3% of
unmodified poly(alkyl ethylenes), 0.001% to 2.5% of stabilizers and
optionally 0.1% to 1% of antistatic materials, 0.2% to 3% of
pigments, 0.05% to 1% of nucleating agents, 5% to 40% of fillers,
2% to 20% of flame retardants and/or 0.001% to 1% of processing
aids also have a better processability than do unmodified
poly(alkyl ethylenes); the .PSI. index for these mixtures is of the
order of 2.times.10.sup.-3 to 7.8.times.10.sup.-3
(kJ/mole/degree).
[0040] As stabilizers, preferably mixtures of 0.01% to 0.6% by
weight of phenolic antioxidants, 0.01% to 0.6% of processing
stabilizers based on phosphites, 0.01% to 0.6% of high-temperature
stabilizers based on disulfides and thioethers and 0.01% to 0.8% of
sterically hindered amines (HALS) are used.
[0041] Suitable phenolic antioxidants are
2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-methylphenol,
2,6-di-t-butyl-4-isoamylphenol, 2,6-di-t-butyl-4-ethylphenol,
2-t-butyl-4,6-diisopropylphenol, 2,6-dicyclopentyl-4-methylphenol,
2,6-di-t-butyl-4-methoxymethylphenol,
2-t-butyl-4,6-dioctadecylphenol, 2,5-di-t-butylhydroquinone,
2,6-di-t-butyl-4,4-hexadecyloxyphenol,
2,2'-methylene-bis(6-t-butyl-4-met- hylphenol),
4,4'-thio-bis-(6-t-butyl-2-methylphenol), octadecyl
3(3,5-di-t-butyl-4-hydroxyphenylpropionate,
1,3,5-trimethyl-2,4,6-tris(3'-
,5'-di-t-butyl-4-hydroxybenzyl)benzene and/or pentaerythritol
tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate.
[0042] As HALS compounds, bis-2,2,6,6-tetramethyl-4-piperidyl
sebacate and/or poly((1,1,3,3-tetramethylbutyl)-imino)-
1,3,5-triazine-2,4,diyl)(2-
,2,6,6-tetramethylpiperidyl)-amino)-hexamethylene-4-(2,2,6,6-tetramethyl)p-
iperidyl)-imino) are particularly suitable.
[0043] As processing aids, calcium stearate, magnesium stearate
and/or waxes can be used.
[0044] Pursuant to the invention, structurally isomeric poly(alkyl
ethylenes) are synthesized either according to an irradiation
method or according to a melt reaction method or according to a
solid phase reaction method.
[0045] For the irradiation, the powdery mixtures of 95% to 99.98%
by weight of poly(C.sub.1 to C.sub.4 alkyl ethylenes) and 0.02% to
5% by weight of acrylic acid, acrylic acid derivatives, allyl
compounds, diacrylates, diallyl compounds, dienes, dimethacrylates,
divinyl compounds, macromers with terminal acrylic, allyl,
isocyanate, oxazoline or vinyl groups based on oligobutadienes,
polysiloxanes or polyethers, monovinyl compounds, polyacrylates,
polymethacrylates and/or triallyl compounds are exposed pursuant to
the invention in a fluidized bed preferably under inert conditions,
at 300.degree. to 500.degree. K, optionally in the presence of
additional conventional auxiliary materials, particularly of 0.01%
to 0.6% by weight of phenolic antioxidants, 0.01% to 0.6% by weight
of high-temperature stabilizers based on disulfides and polyethers,
0.01 to 0.6% of processing stabilizers based on phosphites and/or
0.01% to 0.6% of sterically hindered amines (HALS), 0.1% to 1% of
antistatic agents, 0.2% to 3% pigments, 0.05% to 1% of nucleating
agents, 5% to 40% of fillers, 2% to 20% of flame retardants and/or
0.001% to 1% of processing aids
[0046] a) in a first step of the reaction, preferably in fluidized
bed reactors with continuous feeding of starting materials and
discharging of reaction products, to ionizing radiation having an
energy of 150 to 10,000 KeV at an irradiation dose of 0.5 to 80
KGy, particularly by means of nuclide irradiation equipment with
cobalt 60 as radiation source, by means of electron beam
accelerators of the Cockcroft-Walton type with radiation energies
of 300 to 4500 KeV or by means of electron beam accelerators of the
linear accelerator type with beam current energies of 1,000 to
10,000 KeV, and
[0047] b) in a second step of the reaction, to a thermal treatment
of the irradiated, powdery mixtures at 380.degree. to 550.degree.
K, particularly in extruders at temperatures ranging from
410.degree. to 550.degree. K and at reaction times of 2 to 10
minutes or in the solid phase at temperatures ranging from
380.degree. to 500.degree. K at reaction times from 5 to 60
minutes, it being possible to add, in addition, conventional
stabilizers in concentrations of 0.01% to 0.6% before the thermal
treatment.
[0048] For the melt reaction method, poly(C.sub.1 to C.sub.4 alkyl
ethylenes) are caused to react by a continuous method in the
extruder, preferably under inert conditions,
[0049] a) in the first step of the reaction with 0.01% to 3% by
weight of acyl peroxides, alkyl peroxides, hydroperoxides and/or
peresters, which are either drummed up on the poly(alkyl ethylenes)
in the kneader and metered together or metered as a solution into
the poly(alkyl ethylene) melt in zones 2 to 4 of the extruder),
and
[0050] b) in the second step of the reaction, are caused to react
with 0.01% to 5% by weight of acrylic acid or acrylic acid
derivatives, allyl compounds, diacrylates, diallyl compounds,
dienes, dimethacrylates, divinyl compounds, macromers with terminal
acrylic, allyl, isocyanate, oxazoline or vinyl groups and based on
oligobutadienes, polysiloxanes or polyethers, monovinyl compounds,
polyacrylates, polymethacrylates and/or triallyl compounds, in the
presence of 0.001% to 3.0% by weight of acyl peroxides, alkyl
peroxides, hydroperoxides and/or peresters, and optionally
conventional auxiliary materials, particularly 0.01 to 0.6% by
weight of phenolic antioxidants, 0.01% to 0.6% by weight of
high-temperature stabilizers based on disulfides and polyethers,
0.01% to 0.6% of processing stabilizers based on phosphites and/or
0.01% to 0.8% of sterically hindered amines (HALS), 0.1% to 1% of
antistatic agents, 0.2% to 3% of pigments, 0.05% to 1% of
nucleating agents, 5% to 40% of fillers, 2 to 20% of flame
retardants and/or 0.001% to 1% of processing aids at temperatures
of 140.degree. to 320.degree. C., the radical-forming agents and
the monomers being metered in over separate metering equipment
and/or jointly as a solution into the poly(alkyl ethylene) melt in
zones 3 to 6 of the extruder, optionally with a further portion of
poly(alkyl ethylene).
[0051] For the solid-phase continuous method, preferably under
inert conditions
[0052] a) powdery poly(C.sub.1 to C.sub.4 alkyl ethylenes) are
subjected pursuant to the invention, in a first step of the method
at 290.degree. to 500.degree. K in reactors with rotating equipment
and circulating carrier gas, to a sorption with 0.05 to 3% by
weight of acyl peroxides, alkyl peroxides, hydroperoxides and/or
peresters as well as 0.05% to 5% by weight of acrylic acid, acrylic
acid derivatives, allyl compounds, diacrylates, diallyl compounds,
dienes, dimethacrylates, divinyl compounds, monovinyl compounds,
polyacrylates, polymethacrylates and/or triallyl compounds, which
were introduced over vaporizing equipment into the carrier-gas
stream, and
[0053] b) the powdery mixtures, in a second step of the method,
optionally with the addition of conventional auxiliary materials,
particularly of 0.01% to 2.5% of stabilizers, 0.1% to 1% of
antistatic agents, 0.2% to 3% of pigments, 0.05% to 1% of
nucleating agents, 5% to 40% of fillers, 2% to 20% of flame
retardants and/or 0.001% to 1% of processing aids, are heated in
the feed region of the screw injection molding machine,
particularly twin-screw extruders or single-screw extruders with
plunger screw, to the decomposition temperature of the
radical-forming agent and subsequently melted at reaction
temperatures of 415.degree. to 596.degree. K and granulated.
[0054] As poly(alkyl ethylenes), preferably poly(ethyl ethylenes)
with glass transition temperatures of 242.degree. to 250.degree. K
and molecular weights (M.sub.w) ranging from 2.times. 10.sup.4 to
3.times.10.sup.6, poly(ethyl ethylene co-ethylene) copolymers,
containing 3 to 45 mole percent of ethylene in the copolymer,
poly(ethyl ethylene co-methylethylene) copolymers containing 3 to
97 mole percent of methylethylene in the copolymer,
poly(isobutylenes) with glass transition temperatures of
295.degree. to 303.degree. K and densities ranging from 0.813 to
0.832 g/cc at 25.degree. C., poly(isobutyl ethylene
co-n-butylethylene) copolymers with an n-butylethylene portion of 3
to 97 mole percent, poly(isobutyl ethylene) copolymers with an
ethylene portion in the copolymer of 3 to 45 mole percent,
poly(methyl ethylenes) with glass transition temperatures ranging
from 259.degree. to 268.degree. K and molecular weights (M.sub.w)
ranging from 1.times.10.sup.5 to 8.times.10.sup.6 and/or
poly(methyl ethylene co-ethylene) copolymers with an ethylene
potion in the copolymer of 3 to 45 mole percent, are used.
[0055] The peroxides used are:
[0056] acyl peroxides, such as benzoyl peroxide, 4-chlorobenzoyl
peroxide, 3-methoxybenzoyl peroxide and methylbenzoyl peroxide;
[0057] alkyl peroxides, such as acetyl peroxide, allyloxypropionyl
peroxide, allyl-t-butyl peroxide, benzoyl peroxide,
2,2-bis(t-butylperoxybutane),
1,1-bis-(t-butylperoxy)-3,3,5-trimethylcycl- ohexane,
n-butyl-4,4,bis(t-butylperoxy) valerate, diisopropylaminomethyl-t-
-amyl peroxide, dimethylarninomethyl-t-amyl peroxide,
diethylaminomethyl-t-butyl peroxide, dimethylaminomethyl-t-butyl
peroxide, dinitrobenzoyl peroxide,
1,1-di-(t-amylperoxy)cyclohexane, methoxybenzoyl peroxide,
methylbenzoyl peroxide, t-amyl peroxide, t-butylcumyl peroxide,
t-butylpermaleic acid, t-butyl peroxide, 1-hydroxybutyl-n-butyl
peroxide and/or succinoyl peroxide;
[0058] hydroperoxides, such as decalin hydroperoxide and/or
tetralin hydroperoxide,
[0059] ketone peroxides, such as methyl ethyl ketone
hydroperoxide;
[0060] peresters and peroxycarbonates, such as butyl peracetate,
cumyl peracetate, cumyl perpropionate, cyclohexyl peracetate,
di-t-butyl peradipate, di-t-butyl perazelate, di-t-butyl
perglutarate, di-t-butyl perphthalate, di-t-butyl persebacate,
4-nitrocumyl perpropionate, 1-phenylethyl perbenzoate,
phenylethylnitroperbenzoate, t-butylbicyclo-(2,2,1)
heptapercarboxylate, t-butyl-4-carbomethoxy perbutyrate,
t-butylcyclobutane percarboxylate, t-butylcyclohexyl
peroxycarboxylate, t-butylcyclopentyl percarboxylate,
t-butylcyclopropane percarboxylate, t-butyldimethyl percinnamate,
t-butyl-2-(2,2-diphenylviny- l perbenzoate, t-butyl-4-methoxy
perbenzoate, t-butyl perbenzoate, t-butylcarboxycyclohexane,
t-butyl pernaphthoate, t-butyl peroxyisopropyl carbonate, t-butyl
pertoluate, t-butyl-1-phenylcyclopropyl percarboxylate,
t-butyl-2-propyl 2-perpentenoate, t-butyl- 1-methylcyclopropyl
percarboxylate, t-butyl-4-nitrophenyl peracetate,
t-butylnitrophenyl peroxycarbamate, t-butyl-N-succinimido
percarboxylate, t-butyl percrotonate, t-butyl permaleate, t-butyl
permethacrylate, t-butyl peroctoate, t-butyl
peroxyisopropylcarbonate, t-butyl perisobutyrate, t-butyl
peracrylate and/or t-butyl perpropionate
[0061] The monomers used are
[0062] acrylic acid derivatives, such as acrylamide, acrylonitrile,
benzyl acrylate, butyl acrylate, cyclohexyl acrylate,
N,N-dimethylacrylamide, dodecyl acrylate, ethyl acrylate,
2-ethylhexyl acrylate, 2-ethoxyethyl acrylate, glycidyl acrylate
hydroxyethyl acrylate, isopropyl acrylate, 2-methoxyethyl acrylate,
4-methoxybenzyl acrylate, methyl acrylate, sodium acrylate,
N-t-butoxycarbonyl-2-aminoethyl acrylate, octyl acrylate,
phenylmethyl acrylate, phenyl acrylate, n-propyl acrylate and/or
tetrahydrofurfuryl acrylate;
[0063] diallyl compounds, such as diallyldimethylsilane,
diallyl(2-hydroxy-3-phenoxypropyl) isocyanurate, diallyl cyanurate,
diallylcyanoethyl isocyanurate, diallyl cyanamide, diallyl maleate,
diallylmelamine, diallyl phthalate and/or N,N'-diallyl
tartaramide;
[0064] dimethacrylates, such as ethylene glycol dimethacrylate,
propylene glycol dimethacrylate, trimethylene glycol
dimethacrylate, butylene glycol dimethacrylate, dihydroxypentane
dimethacrylate, dihydroxyhexane dimethacrylate, dihydroxyoctane
dimethacrylate, diglycol dimethacrylate and/or triglycol
dimethacrylate,
[0065] dienes, such as butadiene, butadiene-1-carboxylic acid,
chloroprene, cyclohexadiene, cyclopentadiene,
2,3-dimethylbutadiene, 1-ethoxy butadiene, 1,4-heptadiene,
1,4-hexadiene, 1,6-hexadiene, isoprene, norbornadiene and/or
pentadiene;
[0066] polymethacrylates, such as glycerin trimethacrylate,
trimethylolpropane trimethacrylate and/or pentaerythritol
tetramethacrylate;
[0067] triallyl compounds, such as triallyl citrate, triallyl
cyanurate, triallyl isocyanurate and/or triallylphosphene;
[0068] monovinyl compounds, such as acetoxystyrene, aminostyrene,
t-butylstyrene, bromostyrene, chlorostyrene, dichlorostyrene,
m-diethylaminoethylstyrene, diethylene glycol monovinyl ether,
dimethoxystyrene, dimethylstyrene, ethoxystyrene, ethylstyrene,
ethylvinyl acetate, ethyl vinyl ether, ethylvinyl-pyridine,
fluorostyrene, 2-hydroxybutylstyrene, 2-hydroxypropylstyrene,
m-hydroxystyrene, isopropylstyrene, methoxystyrene,
methylchlorostyrene, .alpha.-methylstyrene, m-methylstyrene,
p-methylstyrene, methylvinylacetyl, methyl vinyl ether,
methylvinylpyridine, 4-phenoxystyrene, phenyl vinyl ether, styrene,
trimethoxy styrene, trimethylstyrene, vinyl acetate, vinyl
acetoxymethyl ketone, vinyl adipate, 9-vinylanthracene, vinyl
benzoate, vinyl butyl ether, vinyl butyl ketone, vinyl butyrate,
vinylcarbazol, vinylcyanoacetate, vinyl dodecyl ether, vinyl ether,
vinylethoxydiethoxysilane, vinyl ethyl ether, vinyl ethylene glycol
glycidyl ether, vinyl ethylhexyl ether, vinyl ethyl ketone, vinyl
formate, vinyl furan, vinyl hexyl ether, vinylimidazole, vinyl
isobutyl ether, vinyl isocyanate, vinyl isopropyl ether, vinyl
isopropyl ketone, vinyl laurate, vinylmethyldiacetoxysilane,
vinylmethyldiethoxysilane, vinyl methyl ether, vinyl methyl ketone,
vinylnapthalene, vinyl octadecyl ether, vinyl octyl ether,
N-vinyloxazolidone, vinyl pelargonate, o-vinylphenol,
vinylphenyldimethylsilane, vinyl phenyl ether, vinyl phenyl ketone,
5-vinylpicoline, vinyl propionate, N-vinylpyridine,
N-vinylpyrrolidone, vinyl stearate, vinyltriethoxysilane,
vinyltrimethoxysilane, vinyltris(trimethoxysiloxy)silane and/or
vinyltrimethylsilane;
[0069] divinyl compounds, such as divinylaniline,
m-divinylbenzenes, p-divinylbenzenes, diethylene glycol divinyl
ether, divinylpentane, divinylpropane and/or
1,3-divinyl-1,1,3,3,-tetramethyldisiloxane;
[0070] allyl compounds, such as allyl acetate, allyl acrylate,
allyl alcohol, allylbenzene, allyl benzyl ether, 3-allyl-1-butene,
allyl butyl ether, allyl cyanurate, allycyclohexane, allyl diethyl
ketone, 4-allyl-2,6-dimethoxyphenol, allyldimethylchlorosilane,
allyl epoxypropyl ether, allyl ethyl ether, allyl glycidyl ether,
allyl glycidyl hexahydrophthalate, allyl glycidyl phthalate, allyl
heptanoate, allyl hexanoate, allyl methacrylate,
allylmethoxyphenol, allyl methyl ether, allyl methyl maleate,
allyloxy-2,3-dihydroxypropane, N-allyl stearamide, allyl tolyl
ether, allyltrichloro-silane, allyltriethoxysilane,
allyltrimethoxysilane, allyltrimethylsilane, allyltriphenylsilane
and/or allyl `vinyl ether;
[0071] diacrylates, such as ethylene glycol diacrylate, propylene
glycol diacrylate, trimethylene glycol diacrylate, butylene glycol
diacrylate, dihydroxypentane diacrylate, dihydroxyhexane
diacrylate, dihydroxyoctane diacrylate, diglycol diacrylate and/or
triglycol diacrylate;
[0072] macromers, based on oligobutadienes, polysiloxanes and/or
polyethers with terminal acrylic, allyl, isocyanate, oxazoline or
vinyl groups.
[0073] As stabilizers, mixtures of 0.01% to 0.6% by weight of
phenolic antioxidants, 0.01% to 0.6% of processing stabilizers
based on phosphites, 0.01% to 0.6% of high-temperature stabilizers
based on disulfides and thioethers and 0.01% to 0.8% of sterically
hindered amines (HALS) are preferably used.
[0074] Suitable phenolic antioxidants are
2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-methylphenol,
2,6-di-t-butyl-4-isoamylphenol, 2,6-di-t-butyl-4-ethylphenol,
2-t-butyl-4,6-diisopropylphenol, 2,6-dicyclopentyl-4-methylphenol,
2,6-di-t-butyl-4-methoxymethylphenol,
2-t-butyl-4,6-dioctadecylphenol, 2,5-di-t-butylhydroquinone,
2,6-di-t-butyl-4,4-hexadecyloxyphenol,
2,2'-methylene-bis(6-t-butyl-4-met- hylphenol),
4,4'-thio-bis-(6-t-butyl-2-methylphenol), octadecyl
3(3,5-di-t-butyl-4-hydroxyphenol)propionate,
1,3,5-trimethyl-2,4,6-tri
s(3',5'-di-t-butyl-4-hydroxybenzyl)benzene and/or pentaerythritol
tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl))-propionate.
[0075] As HALS compounds, bis-2,2,6,6-tetramethyl-4-piperidyl
sebacate and/or
poly-((1,1,3,3-tetramethylbutyl)-imino)-1,3,5-triazine-2,4-diyl)(2-
,2,6,6-tetramethylpiperidyl)-amino)-hexamethylene-4-(2,2,6,6-tetramethyl)p-
iperidyl)-imino) are particularly suitable.
[0076] For the irradiation method, the powdery mixtures are
prepared from 95% to 99.98% by weight of poly(alkyl ethylenes) and
0.02% to 5% by weight of acrylic acid or acrylic acid derivatives,
allyl compounds, diacrylates, diallyl compounds, dienes,
dimethacrylates, divinyl compounds; macromers with terminal
acrylic, allyl, isocyanate, oxazoline or vinyl groups and based on
oligobutadienes, polysiloxanes and/or polyethers, monovinyl
compounds, polyacrylates, polymethacrylates and/or triallyl
compounds, preferably in kneaders, static mixers or fluidized bed
reactors.
[0077] For the melt reaction method, twin-screw extruders with an
L/D ratio of 30 to 45 are preferably used. Advantageous reaction
temperatures for both steps of the reaction are 140.degree. to
250.degree. C. when poly(ethyl ethylene) homopolymers and
copolymers are used, 165.degree. to 270.degree. C. when poly(methyl
ethylene) homopolymers and copolymers are used and 240.degree. to
310.degree. C. when poly(isobutyl ethylene) homopolymers and
copolymers are used.
[0078] For the solid phase reaction method, bunker supply bins are
preferably suitable as reactors with rotating equipment and
circulating carrier gas.
[0079] The inventive poly(alkyl ethylenes) with H and Y structures
and a .PSI. index of 2.times.10.sup.-3 to 8.times.10.sup.-3
(kJ/mole/degree), as well as the mixtures with unmodified
poly(alkyl ethylenes), stabilizers, antistatic agents, pigments,
nucleating agents, fillers, flame retardants and/or processing aids
are preferably suitable for the production of films, sheets,
coatings, pipes, hollow objects and foams.
[0080] The invention is explained by the following examples:
EXAMPLE 1
[0081] To a fluidized bed reactor with a capacity of 15 L, which is
installed in gamma-irradiation equipment of the "gamma beam" type,
2,450 g of powdery poly(ethyl ethylene) homopolymer
(T.sub.g=248.degree. K., M.sub.w=8.times.10.sup.5) are added and
made inert by being fluidized with pure nitrogen. After the
temperature is raised to 90.degree. C., 8.5 g of styrene per hour
are introduced for a period of 8 hours by means of the fluidizing
gas into the reactor in the irradiation position (dose output of
0.55 KGy/hour). After the radiation sources are lowered, the
modified poly(ethyl ethylene) is cooled to 25.degree. C. under an
inert gas, stabilized by metering in 0.35% of a mixture of 0.15%
2-t-butyl-4,6-dimethylphenol and 0.20% of
bis-2,2,6,6-tetramethyl-4-piper- idyl sebacate (as a 10% solution
in acetone) and subjected to a thermal treatment at 162.degree. C.
(residence time: 4.8 minutes) by being extruded in a Werner &
Pfleiderer twin-screw extruder of the ZSK 20 type in a second step
of the reaction. The resulting structurally isomeric poly(ethyl
ethylene) has a .PSI. index of 2.3.times.10.sup.-3 (kJ/mole/degree)
and is present in H and Y structures, wherein
R.sub.1.dbd.R.sub.3.dbd.R.sub.4.dbd.C.sub.2H.sub.5 and
R.sub.2.dbd.R.sub.5.dbd.H, y+z= 345. The proportion of polymeric
bridging elements, determined by IR spectroscopy, and based on the
styrene, is 2.5% by weight.
EXAMPLE 2
[0082] To a fluidized bed reactor, similar to that of Example 1,
3280 g of powdery poly(ethyl ethylene co-ethylene) copolymer (with
an ethylene content of 6 mole percent, a melt index of 3.5 g/10
minutes at 190.degree. C./21, 19 N) are added and made inert by
being fluidized with pure nitrogen. After the temperature is raised
to 80.degree. C., 2.5 g of allyl acrylate per hour are introduced
for a period of 3.5 hours by means of the fluidizing gas into the
reactor in the irradiation position (dose output of 0.55 KGy/hour).
After the radiation sources are lowered, the modified poly(ethyl
ethylene co-ethylene) is cooled to 25.degree. C. under an inert
gas, stabilized by metering in 0.45% of a mixture of 0.25%
2,6-di-t-butyl-4-methylphenol and 0.20% of
bis-2,2,6,6-tetramethyl-4-pipe- ridyl sebacate (as a 10% solution
in acetone) and subjected to a thermal treatment at 166.degree. C.
(residence time: 4.2 minutes) by being extruded in a Werner &
Pfleiderer twin-screw extruder of the ZSK 20 type in a second step
of the reaction. The resulting structurally isomeric poly(ethyl
ethylene co-ethylene) copolymer has a .PSI. index of
3.4.times.10.sup.-3 (kJ/mole/degree) and is present in H and Y
structures, wherein R.sub.1.dbd.R.sub.3.dbd.C.sub.2H.sub.5 and
R.sub.2.dbd.R.sub.4.dbd.R.sub.5.dbd.H, y+z=295. The proportion of
polymeric bridging elements, determined by IR spectroscopy and
based on the allyl acrylate, is 0.22% by weight; the t/u ratio is
about 16.
EXAMPLE 3
[0083] Into a fluidized bed reactor, similar to that of Example 1,
3960 g of a poly(isobutyl ethylene) homopolymer
(T.sub.g=300.degree. K, M.sub.w=6.times.10.sup.5) are metered and
made inert by being fluidized with pure nitrogen. After the
temperature is raised to 140.degree. C., 4.9 g of glycidyl acrylate
per hour are introduced for a period of 5.3 hours by means of the
fluidizing gas into the reactor in the irradiation position (dose
output of 0.55 KGy/hour). After the radiation sources are lowered,
the modified poly(isobutyl ethylene) is kept for a further hour at
140.degree. C. under an inert gas and cooled to 25.degree. C. and
stabilized by metering in 0.40% of a mixture of 0.20%
2-t-butyl-4,6-dioctadecylphenol and 0.20% of
bis-2,2,6,6-tetramethyl-4-pi- peridyl sebacate (as a 10% solution
in acetone). The resulting structurally isomeric poly(isobutyl
ethylene) has a .PSI. index of 3.2.times.10.sup.-3 (kJ/mole/degree)
and is present in H and Y structures, wherein
R.sub.1.dbd.R.sub.3.dbd.R.sub.4.dbd.i-C.sub.4H.sub.9 and
R.sub.2.dbd.R.sub.5.dbd.H, y+z=173. The proportion of polymeric
bridging elements, determined by IR spectroscopy on the basis of
glycidyl acrylate, is 0.58% by weight.
EXAMPLE 4
[0084] In a kneader under nitrogen, 0.15% of
2,6-dicyclopentyl-4-methylphe- nol, 0.15% of
bis-2,2,6,6-tetramethyl-4-piperidyl sebacate and 3.2% of t-butyl
acrylate are drummed up on a poly(ethyl ethylene) homopolymer
(T.sub.g=248.degree. K, M.sub.w=4.times.10.sup.5). The powdery
mixture is irradiated in a fluidized bed reactor with a
Cockroft-Walton type electron beam accelerator with a radiation
energy at 3,500 KeV of 2.times.35 KW. The two beam-emerging windows
of the scanner are integrated in the narrow side surfaces of the
fluidized bed reactor (capacity 0.3 m.sup.3, bottom, against which
there is a flow 0.95.times.0.20 m). At an irradiation temperature
of 110.degree. C., the powdery mixture is charged into and
discharged out of the fluidized bed reactor continuously at a
throughput of 0.5 kg/second and subsequently, in a second step of
the reaction, subjected in a Werner & Pfleiderer ZSK 120
twin-screw extruder under inert conditions to a thermal treatment
at 165.degree. C. (residence time 6.3 minutes). The resulting
structurally isomeric poly(ethyl ethylene) homopolymer has a .PSI.
index of 3.2.times. 10.sup.-3 (kJ/mole/degree) and exists in H and
Y structures, with
R.sub.1.dbd.R.sub.3.dbd.R.sub.4.dbd.C.sub.2H.sub.5,
R.sub.2.dbd.R.sub.4.dbd.H and y+z=310 and w=620. The proportion of
polymeric bridging elements, based on t-butyl acrylate, is
2.65%.
EXAMPLE 5
[0085] In a kneader under nitrogen, 0.31% of
2,6-di-t-butyl-4-methoxymethy- lphenol, 0.15% of
bis-2,2,6,6-tetramethyl-4-piperidyl sebacate and 0.35% of
divinylbenzene are drummed up on poly(methyl ethylene) homopolymer
(T.sub.g=263.degree. K, M.sub.w=6.times.10.sup.5). The powdery
mixture is irradiated in the 0.3 m.sup.3 fluidized bed reactor with
the electron beam accelerator of Example 4. At an irradiation
temperature of 110.degree. C., the powdery mixture is charged into
and discharged out of the fluidized bed reactor continuously at a
throughput of 1.5 kg/second and subsequently, in a second step of
the reaction, subjected in a Werner & Pfleiderer ZSK 120
twin-screw extruder under inert conditions to a thermal treatment
at 220.degree. C. (residence time 4.9 minutes) The resulting
structurally isomeric poly(methyl ethylene) has a .PSI. index of
4.1.times.10.sup.-3 (kJ/mole/degree) and exists in H and Y
structures, with R.sub.1.dbd.R.sub.3.dbd.R.sub.4.dbd.CH.sub.3,
R.sub.2.dbd.R.sub.5.dbd.H and y+z=540. The proportion of polymeric
bridging elements, based on divinylbenzene and determined by IR
spectroscopy, is 0.32%.
EXAMPLE 6
[0086] In a kneader under nitrogen, 0.15% of
2,6-di-t-butyl-4-methoxymethy- lphenol, 0.15% of
bis-2,2,6,6-tetramethyl-4-piperidyl sebacate and 1.2% of
vinyltrimethylsilane are drummed up on poly(ethyl ethylene
co-phenylethylene) copolymer (phenylethylene content 5 mole
percent, melt index 6.8 g/10 minutes at 190.degree. C./21.19 N).
The powdery mixture is irradiated in the 0.3 m.sup.3 fluidized bed
reactor with the electron beam accelerator of Example 4. At an
irradiation temperature of 65.degree. C., the powdery mixture is
charged into and discharged out of the fluidized bed reactor
continuously at a throughput of 0.7 kg/second and subsequently, in
a second step of the reaction subjected in a Werner &
Pfleiderer ZSK 120 twin-screw extruder under inert conditions to a
thermal treatment at 170.degree. C. (residence time 5.2 minutes).
The resulting structurally isomeric poly(ethyl ethylene
co-phenylethylene) copolymer has a .PSI. index of
3.7.times.10.sup.3 (kJ/mole/degree) and exists in H and Y
structures, with R.sub.1.dbd.R.sub.3.dbd.C.sub.2H.sub.5- ,
R.sub.2.dbd.R.sub.5.dbd.H, R.sub.4.dbd.C.sub.2H.sub.5 and y+z=215.
The proportion of polymeric bridging elements, based on
vinyltrimethylsilane and determined by IR spectroscopy, is 0.95%
and the t/u ratio is about 19.
EXAMPLE 7
[0087] In a kneader under nitrogen, 0.6% of allyl methacrylate is
drummed up on poly(isobutyl ethylene co-ethylene) copolymer
(ethylene content 8 mole percent, melt index 0.8 g/10 minutes at
230.degree. C.). The powdery mixture is irradiated in a fluidized
bed reactor equipped with a linear electron accelerator equipped
with 3 scanners (with a beam current energy of 8,000 KeV and a beam
power of 3.times.5 KW). The bottom of the fluidized bed reactor
(capacity of 0.94 m.sup.3), against which there is flow, has the
shape of an equilateral triangle with a side length of 1.3 m.
Beam-emerging windows of the scanner are integrated in the three
side surfaces. At an irradiation temperature of 175.degree. C., the
powdery mixture is charged into and discharged out of the fluidized
bed reactor continuously at a throughput of 40 kg/minute and
subsequently, in a second step of the reaction, with addition of
0.15% of 2,6-di-t-butyl-4-methoxy-methylphenol and 0.15% of
bis-2,2,6,6-tetramethyl-4-piperidyl sebacate, subjected in a Werner
& Pfleiderer ZSK 120 twin-screw extruder under inert conditions
to a thermal treatment at 255.degree. C. (residence time 4.2
minutes). The resulting structurally isomeric poly(isobutyl
ethylene co-ethylene) copolymer has a .PSI. index of
3.4.times.10.sup.-3 (kT/mole/degree) and exists in H and Y
structures, with R.sub.1.dbd.R.sub.3.dbd.i-C.sub.4H.sub- .9,
R.sub.2.dbd.R.sub.5.dbd.R.sub.4.dbd.H and y+z=250. The proportion
of polymeric bridging elements, based on allyl methacrylate and
determined by IR spectroscopy, is 0.56% and the t/u ratio is about
11.5.
EXAMPLE 8
[0088] In a kneader under nitrogen, 0.25% of glycerin
trimethacrylate and 0.65% of behenic acid are drummed up on
poly(methyl ethylene co-ethylene) copolymer (ethylene content of
7%, M.sub.w=3.5.times.10.sup.-5). The powdery mixture is irradiated
in a fluidized bed reactor with the irradiating facilities of
Example 7 at a throughput of 35 kg/minute and an irradiation
temperature of 125.degree. C. After the addition of 0.2% of
4,4'-thio-bis-(6-t-butyl-2-methylphenol) and 0.15% of poly-(1,1,3,3
-tetramethylbutyl)-imino)-
1,3,5-triazine-2,4-diyl)(2,2,6,6-tetramethylpi-
peridyl)-amino)-hexamethylene-4-(2,2,6,6-tetramethyl)piperidyl)-imino),
the powdery mixture, in a second step of the reaction, is subjected
in a Werner & Pfleiderer ZSK 120 twin-screw extruder under
inert conditions to a thermal treatment at 215.degree. C.
(residence time 4.6 minutes). The resulting structurally isomeric
poly(methyl ethylene co-ethylene) copolymer has a .PSI. index of
4.4.times.10.sup.-3 (kJ/mole/degree) and exists in H and Y
structures, with R.sub.1.dbd.R.sub.3.dbd.CH.sub.3,
R.sub.2.dbd.R.sub.4.dbd.R.sub.5.dbd.H, and y+z=350. The proportion
of polymeric bridging elements, based on glycerin trimethacrylate,
is 0.95% and the t /u ratio is about 0.24.
EXAMPLE 9
[0089] In a kneader under nitrogen, 0.32% of allyl glycidyl
phthalate are drummed up under nitrogen on powdery poly(ethyl
ethylene co-methylene) copolymer (methylene content of 92 mole
percent, melt index 1.8 g/10 min at 230.degree. C./21.19 N). The
powdery mixture is irradiated in a fluidized bed reactor with the
irradiating facilities of Example 7 at a throughput of 37 kg/minute
and an irradiation temperature of 125.degree. C. After the addition
of 0.2% of 4,4'-thio-bis-(6-t-butyl-2-methylphenol) and 0.15% of
poly-((1,1,3,3-tetramethylbutyl)-imino)-1,3,5-triazine,2,4-d-
iyl)-(2,2,6,6,-tetra-methylpiperidyl)-amino)-hexamethylene-4-(2,2,6,6-tetr-
amethyl)piperidyl)-imino), the powdery mixture, in a second step of
the reaction, is subjected in a Werner & Pfleiderer ZSK 120
twin-screw extruder under inert conditions to a thermal treatment
at 205.degree. C. (residence time 4.8 minutes) The resulting
structurally isomeric poly(ethyl ethylene co-methylene) copolymer
has a .PSI. index of 4.1.times.10.sup.-3 (kJ/mole/degree) and
exists in H and Y structures, with
R.sub.1.dbd.R.sub.3.dbd.C.sub.2H.sub.5, R.sub.2.dbd.R.sub.5.dbd.H,
R.sub.4.dbd.CH.sub.3 and y+z= 770. The proportion of polymeric
bridging elements, based on glycerin trimethacrylate and determined
by IR spectroscopy, is 0.30% by weight and the t/u ratio is about
0.08.
EXAMPLE 10
[0090] In a kneader under nitrogen, 0.22% of ethylene glycol
diacrylate are drummed up on powdery poly(isobutyl ethylene
co-n-butylethylene) copolymer (n-butylethylene content of 42 mole
percent, melt index 0.9 g/10 min at 230.degree. C./49 N). The
powdery mixture is conveyed pneumatically by inert gas into a
0.20.times.3.50 m.sup.2 cassette reactor with 4 integrated cathodes
of a low energy accelerator of the band beam type (with an electron
energy of 250 KeV and a radiation output of 4.times.10 kW) and
integrated vibration equipment. The throughput at an irradiation
temperature of 160.degree. C. is 43 kg/minute. After the addition
of 0.18% of 2,6-di-t-butyl-4-methoxymethylphenol and 0.15% of
bis-2,2,6,6-tetramethyl-4-piperidyl sebacate, the powdery mixture,
in a second step of the reaction, is subjected in a Werner &
Pfleiderer ZSK 120 twin-screw extruder under inert conditions to a
thermal treatment at 255.degree. C. (residence time 5.3 minutes).
The resulting mixture of unmodified and structurally isomeric
poly(isobutylene ethylene co-n-butylethylene) copolymer has a .PSI.
index of 3.1.times.10.sup.-3 (kJ/mole/degree). The structurally
isomeric poly(alkyl ethylene) exists in H and Y structures, with
R.sub.1.dbd.R.sub.3.dbd.i-C.sub.4H.sub.9,
R.sub.2.dbd.R.sub.5.dbd.H, R.sub.4.dbd.n-C.sub.4H.sub.9 and y+
z=410. The proportion of polymeric bridging elements, based on
ethylene glycol diacrylate and determined by IR spectroscopy, is
0.21% by weight and the t/u ratio is about 1.4.
EXAMPLE 11
[0091] In a cassette reactor with radiation facilities of Example
10, a poly(methyl ethylene) homopolymer
(M.sub.w=4.9.times.10.sup.5, T.sub.g=265.degree. K) is conveyed by
means of a carrier gas of 97% pure nitrogen and 3% butadiene. The
throughput of the fluidized bulk material layer at an irradiation
temperature of 160.degree. C. is 31 kg/minute. After the addition
of 0.45% of 0.25% of 2,6-di-t-butyl-4-methylphenol and 0.20% of
bis-2,2,6,6-tetramethyl-4-piperidyl sebacate, the powdery mixture,
in a second step of the reaction, is subjected in a Werner &
Pfleiderer ZSK 120 twin-screw extruder under inert conditions to a
thermal treatment at 200.degree. C. (residence time 5.1 minutes).
The resulting mixture of structurally isomeric poly(methyl
ethylene) and the unmodified poly(methyl ethylene) homopolymer has
a .PSI. index of 2.9.times.10.sup.-3(kJ/mole/degree) and an M.sub.n
value of 7.7.times.10.sup.4
EXAMPLE 12
[0092] In a kneader under nitrogen, 3.9% of methyl methacrylate are
drummed up on powdery poly(ethyl ethylene-co-chloroethylene)
copolymer (chloroethylene content of 4 mole percent, melt index 3.2
g/10 min at 190.degree. C./21.19 N) and conveyed pneumatically into
the cassette reactor with radiation facilities of Example 10. The
throughput of the fluidized bulk material layer at an irradiation
temperature of 60.degree. C. is 18 kg/minute. After the addition of
0.40% of a mixture of 0.25% 2,6-di-t-butyl-4-methylphenol and 0.15%
of bis-2,2,6,6-tetramethyl-4-pipe- ridyl sebacate, the powdery
mixture, in a second step of the reaction, is subjected in a Werner
& Pfleiderer ZSK 120 twin-screw extruder under inert conditions
to a thermal treatment at 165.degree. C. (residence time 5.9
minutes). The resulting mixture of unmodified and structurally
isomeric poly(ethyl ethylene co-n-chloroethylene) copolymer has a
.PSI. index of 2.6.times.10.sup.-3 (kJ/mole/degree). The modified
poly(alkyl ethylene) exists in H and Y structures, with
R.sub.1.dbd.R.sub.3.dbd.i-C.- sub.4H.sub.9,
R.sub.2.dbd.R.sub.5.dbd.H, R.sub.4.dbd.Cl and y+z=325. The
proportion of polymeric bridging elements, based on methyl
methacrylate, is 3.1% by weight.
EXAMPLE 13
[0093] The structurally isomeric poly(ethyl ethylene) of Example 1
(40 parts) is mixed with 60 parts of unmodified poly(butyl
ethylene), 0.23 parts of 2-t-butyl-4,6-dimethylphenol, 0.10 parts
of behenic acid, 0.20 parts of calcium stearate and 0.20 parts of
poly-((
1,1,3,3-tetramethylbutylimino)triazine-2,4,diyl)-(2,2,6,6,-tetramethylpip-
eridyl)-amino)-hexamethylene-4-(2,2,6,6-tetramethyl)piperidyl)imino)
and homogenized in the extruder at
140.degree./165.degree./175.degree./175.de-
gree./170.degree./155.degree. C. The resulting compounds has a
.PSI. index of 2.7.times.10.sup.-3 (kJ/mole/degree).
EXAMPLE 14
[0094] The structurally isomeric poly(alkyl ethylenes) of Examples
5, 8 and 9 (20 parts of each) are homogenized with 15 parts of an
unmodified poly(methyl ethylene co-ethylene) copolymer having an
ethylene content of 50%, 15 parts of an unmodified poly(ethyl
ethylene co-methylethylene) copolymer having an ethylene content of
15%, 8 parts of talcum and 1 part of carbon black in the extruder
at 140.degree./190.degree./230.degree./22-
0.degree./220.degree./210.degree./200.degree. C. The alloy has a
.PSI. index of 2.4.times.10.sup.-3 (kJ/mole/degree).
EXAMPLE 15
[0095] The structurally isomeric poly(isobutyl ethylene
co-ethylene) copolymer of Example 7 is extruded in the extruder
with a fishtail die at 255.degree. to 275.degree. C. into panels.
Milled out test pieces have the following characteristic values:
tensile strength: 27 MPa, elongation at break: 18%, modulus of
tension: 1.6 GPa, modulus of bending: 1.4 GPa. The corresponding
characteristic values for the unmodified poly(isobutyl ethylene)
are 23 MPa, 16%, 1.2 GPa and 1.1 GPa.
EXAMPLE 16
[0096] In a Werner & Pfleiderer ZSK 30 twin-screw extruder,
LID=42, with inert gas flow, vacuum degassing and strand
granulation and having a temperature profile of
140.degree./170.degree./165.degree./190.degree./16-
5.degree./190.degree./145.degree., a poly(ethyl ethylene)
homopolymer (T.sub.g=248.degree. K, M.sub.w=8.times.10.sup.5) is
metered at the rate of 16 kg/h. Into the melt in zone 3, a 20%
solution of t-butyl perbenzoate in acetone is added at the rate of
0.64 L/h. In zone 5, vinyl trimethoxysilane, at a rate of 0.61 L/h,
and a 20% solution of t-butyl perbenzoate in acetone, at a rate of
0.64 L/h, are metered in over separate metering pumps. The
resulting structurally isomeric poly(ethyl ethylene) has a .PSI.
index of 3.3.times.10.sup.-3 (kJ/mole/degree) and exists in H and Y
structures. R.sub.1.dbd.R.sub.3.dbd.R.sub.4.dbd.C.sub.2- H.sub.5
and R.sub.2.dbd.R.sub.5.dbd.H and y+z=380. The proportion of
polymeric bridging elements, based on vinyltrimethoxysilane and
determined by IR spectroscopy, is 3.2% by weight.
EXAMPLE 17
[0097] Into a Werner & Pfleiderer twin-screw extruder of
Example 16, having a temperature profile of
140.degree./170.degree./165.degree./190.d-
egree./165.degree./190.degree./145.degree., a poly(ethyl ethylene
co-ethylene) copolymer, with an ethylene content of 6 mole percent
and a melt index of 3.5 g/10 min at 190.degree. C./21.19 N, is
added at the rate of 12 kg/h. To the melt in zone 3, a 10% solution
of t-butyl pertoluate in acetone is added at a rate of 0.48 L/h. In
zone 5, allyl methyl maleate, at a rate of 0.11 L/h, and a 10%
solution of t-butyl pertoluate in acetone, at a rate of 0.84 L/h,
are added over separate metering pumps. The resulting structurally
isomeric poly(ethyl ethylene co-ethylene) copolymer has a .PSI.
index of 3.1.times.10.sup.-3 (kJ/mole/degree) and exists in H and Y
structures, R.sub.1.dbd.R.sub.3.dbd.C.sub.2H.sub.5 and
R.sub.2.dbd.R.sub.4.dbd.R.sub.- 5.dbd.H and y+z=275. The proportion
of polymeric bridging elements, based on allyl methyl maleate and
determined by IR spectroscopy, is about 0.75% by weight and the t/u
ratio is about 16.
EXAMPLE 18
[0098] Into a Werner & Pfleiderer twin-screw extruder of
Example 16, having a temperature profile of
140.degree./175.degree./190.degree./165.d-
egree./190.degree./180.degree./145.degree., a poly(ethyl ethylene
co-methylethylene) copolymer, with a methylethylene content of 92
mole percent and a melt index of 1.8 g/10 min at 230.degree. C.
/21.19 N, onto which 0.17% of 3-methoxybenzoyl peroxide was drummed
in the kneader, is added at the rate of 21 kg/h. In zone 4 of the
extruder, a 20% solution of 3-methoxybenzoyl peroxide in methyl
ethyl ketone, at a rate of 0.18 L/h, and allyl glycidyl hexyl
hydrophthalate, at a rate of 0.16 L/h, are added over separate
metering pump. The resulting structurally isomeric poly(ethyl
ethylene co-methylethylene) copolymer has a .PSI. index of
4.1.times.10.sup.-3 (kJ/mole/degree) and exists in H and Y
structures. R.sub.1.dbd.R.sub.3.dbd.C.sub.2H.sub.5 and
R.sub.2.dbd.R.sub.5.dbd.H, R.sub.4.dbd.CH.sub.3 and y+z=790. The
proportion of polymeric bridging elements, based on allyl glycidyl
hexyl hydrophthalate, is about 0.62% by weight and the t/u ratio is
about 0.08.
EXAMPLE 19
[0099] Into a Wemer & Pfleiderer twin-screw extruder of Example
16, having a temperature profile of
245.degree./270.degree./280.degree./260.degree./-
280.degree./270.degree./250.degree., a poly(isobutyl ethylene)
homopolymer (T.sub.g=300.degree. K, M.sub.w=6.times.10.sup.5), onto
which 0.18% of t-butyl peroxide was drummed, is added at the rate
of 18 kg/h to the feeding funnel of the twin-screw extruder. In
zone 4 of the extruder, a 10% solution of t-butyl cumyl peroxide in
diethyl ketone, at a rate of 0.34 L/h, and diallyl phthalate, at a
rate of 0.12 L/h, are added over separate metering pumps. The
resulting structurally isomeric poly(isobutyl ethylene) has a A
index of 3.6.times.10.sup.-3 (kJ/mole/degree) and exists in H and Y
structures. R.sub.1.dbd.R.sub.3.dbd.R.sub.4.dbd.i-C.sub.4H.sub.9
and R.sub.2.dbd.R.sub.5.dbd.H and y+z=190. The proportion of
polymeric bridging elements, based on diallyl phthalate and
determined by IR spectroscopy, is about 0.52% by weight.
EXAMPLE 20
[0100] Into a Werner & Pfleiderer twin-screw extruder of
Example 16, having a temperature profile of
170.degree./205.degree./185.degree./170.d-
egree./210.degree./170.degree./160.degree., a poly(methyl ethylene)
homopolymer (T.sub.g=263.degree. K, M.sub.w=6.1.times.10.sup.5),
onto which 0.31% of 2,6-di-t-butyl-4-methoxymethylphenol was
drummed in the kneader, is added at the rate of 14 kg/h to the
feeding funnel of the twin-screw extruder In zone 4 of the
extruder, a 10% solution of benzoyl peroxide in acetone, at a rate
of 0.36 L/h, and divinyl benzene, at a rate of 0.042 L/h, are added
over separate metering pumps. The resulting structurally isomeric
poly(methyl ethylene) has a .PSI. index of 3.9.times.10.sup.-3
(kJ/mole/degree) and exists in H and Y structures.
R.sub.1.dbd.R.sub.3.dbd.R.sub.4.dbd.CH.sub.3 and
R.sub.2.dbd.R.sub.5.dbd.- H and y+z=580. The proportion of
polymeric bridging elements, based divinylbenzene and determined by
IR spectroscopy, is about 0.27% by weight.
EXAMPLE 21
[0101] Into a Werner & Pfleiderer twin-screw extruder of
Example 16, having a temperature profile of
220.degree./260.degree./245.degree./280.d-
egree./245.degree./270.degree./235.degree., a poly(isobutyl
ethylene co-n-butylethylene) copolymer, with a butylethylene
content of 42 mole percent and a melt index of 0.9 g/10 min at
230.degree. C./49 N, is added at the rate of 19.5 kg/h to the
feeding funnel of the twin-screw extruder. Into the melt in zone 3,
a 20% solution of cumyl hydroperoxide in acetone as added at the
rate of 0.195 L/h. In zone 5 of the extruder, a 20% solution of
cumyl hydroperoxide in acetone, at a rate of 0.14 L/h, and
dihydroxyoctane dimethacrylate, at a rate of 0.23 L/h, are added
over separate metering pumps. The resulting structurally isomeric
poly(isobutyl ethylene co-n-butylethylene) copolymer has a .PSI.
index of 3.7.times.10.sup.-3 (kJ/mole/degree) and exists in H and Y
structures. R.sub.1.dbd.R.sub.3.dbd.i-C.sub.4H.sub.9 and
R.sub.2.dbd.R.sub.5.dbd.H, R.sub.4.dbd.n-C.sub.4H.sub.9 and
y+z=410. The proportion of polymeric bridging elements, based on
dihydroxyoctane dimethacrylate, is about 1.05% by weight and the
t/u ratio is about 1.4.
EXAMPLE 22
[0102] Into a Werner & Pfleiderer twin-screw ZSK 53 extruder,
LAD=36, with inert gas flow, vacuum, degassing and underwater
granulation and having a temperature profile of
140.degree./165.degree./155.degree./180.degree./15-
5.degree./185.degree./155.degree., a poly(ethyl ethylene
co-phenylethylene) copolymer, with a phenylethylene content of 5
mole percent and a melt index of 6.8 g/10 min at 190.degree.
C./21.19 N, is added at the rate of 32 kg/h to the feeding funnel
of the twin-screw extruder. Into the melt in zone 3, a 20% solution
of decalin hydroperoxide in methyl ethyl ketone is added at a rate
of 0.16 L/h. In zone 5 of the extruder, a 20% solution of decalin
hydroperoxide, at the rate of 0.14 L/h, and a 50% solution of
glycidyl acrylate in ethanol, at a rate of 0.29 L/h, are added over
separate metering pumps. The resulting structurally isomeric
poly(ethyl ethylene co-phenylethylene) copolymer has a .PSI. index
of 4.03.times.10.sup.-3 (kJ/mole/degree) and exists in H and Y
structures. R.sub.1.dbd.R.sub.3.dbd.C.sub.2H.sub.5 and
R.sub.2.dbd.R.sub.5.dbd.H, R.sub.4.dbd.C.sub.2H.sub.5 and y+z=240.
The proportion of polymeric bridging elements, based on glycidyl
acrylate, is about 0.43% and the t/u ratio is about 19.
EXAMPLE 23
[0103] Into a Werner & Pfleiderer twin-screw extruder of
Example 22 and having a temperature profile of
245.degree./27.degree./255.degree./28.deg-
ree./285.degree./280.degree./250.degree., a poly(isobutyl ethylene
co-ethylene) copolymer, with an ethylene content of 8 mole percent
and a melt index of 0.8 g/10 min at 230.degree. C., is added at the
rate of 38 kg/h to the feeding funnel of the twin-screw extruder.
Into the melt in zone 3, a 20% solution of t-butyl hydroperoxide in
diethyl ketone is added at a rate of 1.71 L/h. In zone 5 of the
extruder, a 20% solution of t-butylcumyl peroxide in methyl ethyl
ketone, at a rate of 0.95 L/h, and a liquid polyether based on
polyethylene glycol with terminal allyl groups, having a molecular
weight of 1450, at a rate of 1.71 L/h, are added over separate
metering pumps. The resulting structurally isomeric
poly(isobutylene co-ethylene) copolymer has a .PSI. index of
3.8.times.10.sup.-3 (kJ/mole/degree) and exists in H and Y
structures. R.sub.1.dbd.R.sub.3.dbd.i-C.sub.4H.sub.9, and
R.sub.2.dbd.R.sub.5.dbd.R.s- ub.4.dbd.H and y+z=270. The proportion
of polymeric bridging elements, based on the polyether with
terminal allyl groups and determined by IR spectroscopy, is about
4.1% and the t/u ratio is about 11.5.
EXAMPLE 24
[0104] Into a Werner & Pfleiderer twin-screw extruder of
Example 22, having a temperature profile of
70.degree./200.degree./230.degree./230.de-
gree./210.degree./200.degree./200.degree., a poly(methyl ethylene)
homopolymer (T.sub.g=265.degree. K, M.sub.w=4.9.times.10.sup.5),
onto which a mixture of 0.1% of t-butylperoxybenzoate, 0.2% of
1,3-propylene glycol
benzenepropionate-3,5-bis(1,1-dimethylethyl)-4-hydroxy-2,2-bis((3
-(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)-1-oxopropyl)-methyl)
and 0.1% of di-t-butylhydroxytoluene were drummed, is added at the
rate of 14.4 kg/h to the feeding funnel of the twin-screw extruder.
Into the metering opening of zone 3, a mixture of a poly(methyl
ethylene) homopolymer with 0.2% of t-butyl peroxybenzoate and 0.3%
divinylbenzene is added at the rate of 21.6 kg/h. The resulting
blend of structurally isomeric poly(methyl ethylene) and the
unmodified poly(methyl ethylene) homopolymer has a .PSI. index of
4.2.times.10.sup.-3 (kJ/mole/degree) and an M.sub.n value of
7.4.times.10.sup.4.
EXAMPLE 25
[0105] Into a Werner & Pfleiderer twin-screw extruder of
Example 22 and having a temperature profile of
140.degree./165.degree./180.degree./155.d-
egree./185.degree./185.degree./155.degree., a poly(ethyl ethylene
co-chloroethylene) copolymer, with a chlorine content of 4 mole
percent and a melt index of 3.2 g/10 min at 190.degree. C./21.19 N,
onto which 0.026 kg of t-butyl perbenzoate and 0.084 kg of calcium
stearate were drummed in the kneader, is added at the rate of 43
kg/h to the feeding funnel of the twin-screw extruder. To zone 4 of
the extruder, a 20% solution of cumyl peroxide in acetone, at the
rate of 0.066 L/h, and a 10% solution of triallyl isocyanurate in
acetone, at the rate of 2.36 L/h, are added over separate metering
pumps. The resulting structurally isomeric poly(ethyl ethylene
co-chloroethylene) copolymer has a .PSI. index of
3.6.times.10.sup.-3 (kJ/mole/degree) and exists in H and Y
structures. R.sub.1R.sub.3.dbd.i-C.sub.4H.sub.9, and
R.sub.2.dbd.R.sub.5H, R.sub.4.dbd.Cl and y+z=310. The proportion of
polymeric bridging elements, on the basis of triallyl isocyanurate,
is 0.53%.
EXAMPLE 26
[0106] Into a Werner & Pfleiderer twin-screw extruder of
Example 22 and having a temperature profile of
180.degree./210.degree./230.degree./195.d-
egree./235.degree./235.degree./190.degree., a poly(methyl ethylene
co-ethylene) copolymer, with an ethylene content of 7% and an
M.sub.w of 3.5.times.10.sup.5, onto which 0.123 kg of
2-t-butyl-4-methylphenol and 0.185 kg of behenic acid were drummed
in the kneader, is added at the rate of 39 kg/h to the feeding
funnel of the twin-screw extruder. In zone 4 of the extruder, a 20%
solution of di-t-butyl peradipate in methyl ethyl ketone, at the
rate of 0. 154 L/h, and a 50% solution of trimethylolpropane
trimethacrylate, at the rate of 0.115 L/h, are added over separate
metering pumps. The resulting structurally isomeric poly(methyl
ethylene co-ethylene) copolymer has a .PSI. index of
4.8.times.10.sup.-3 (kJ/mole/degree) and exists in H and Y
structures. R.sub.1.dbd.R.sub.3.dbd.CH.sub.3,
R.sub.2.dbd.R.sub.4.dbd.R.sub.5.dbd.H and y+z=340 and w=680. The
proportion of polymeric bridging elements, on the basis of
trimethylolpropane trimethacrylate, is 0.15%.
EXAMPLE 27
[0107] Into a Werner & Pfleiderer twin-screw extruder of
Example 22 and having a temperature profile of
140.degree./170.degree./190.degree./165.d-
egree./185.degree./180.degree./155.degree., a poly(ethyl ethylene)
homopolymer, (T.sub.g=248.degree. K, M.sub.w=4.times.10.sup.6), on
which 0.066 kg of t-butyl pertoluate and 0.045 kg of bis
2,2,6,6-tetramethyl-4-piperidyl sebacate were drummed, is added at
the rate of 33 kg/h to the feeding funnel of the twin-screw
extruder. To zone 4 of the extruder, a 25% solution of t-butyl
pertoluate in acetone, at the rate of 0.26 L/h, and ethylhexyl
acrylate, at the rate of 1.15 L/h, are added over separate metering
pumps. The resulting structurally isomeric poly(ethyl ethylene)
homopolymer has a .PSI. index of 3.4.times.10.sup.-3
(kJ/mole/degree) and exists in H and Y structures.
R.sub.1.dbd.R.sub.3.dbd.R.sub.4.dbd.C.sub.2H.sub.5,
R.sub.2.dbd.R.sub.4.dbd.H and y+z=340 and w=680. The proportion of
polymeric bridging elements, on the basis of ethylhexyl acrylate,
is 0.15%.
EXAMPLE 28
[0108] The structurally isomeric poly(ethyl ethylene) of Example 16
(40 parts) is mixed with 60 parts of unmodified poly(butyl
ethylene), 0.23 parts of 2-t-butyl-4,6-dimethylphenol, 0.10 parts
of behenic acid, 0.20 parts of calcium stearate and 0.20 parts of
poly-((1,3,3-tetramethylbutyl-
)-imino)-triazine-2,4-diyl)-(2,2,6,6-tetramethylpiperidyl)-amino)-hexameth-
ylene-4-(2,2,6,6-tetramethyl)piperidyl)imino) and homogenized in
the extruder at
140.degree./165.degree./175.degree./175.degree./175.degree./1-
70.degree./155.degree. C. The resulting compound has a .PSI. index
of 2.9.times.10.sup.-3 (kJ/mole/degree).
EXAMPLE 29
[0109] The structurally isomeric poly(alkyl ethylenes) of Examples
20, 24, 26 (22 parts of each) are mixed with 15 parts of an
unmodified poly(methyl ethylene co-ethylene) copolymer containing
50% of ethylene, 10 parts of an unmodified poly(ethyl ethylene
co-methylethylene) copolymer containing 15% ethylene, 8 parts of
talcum and 1 part of carbon black are homogenized in the extruder
at 140.degree./190.degree./230.degr-
ee./220.degree./220.degree./210.degree./200.degree. C. The alloy
has a .PSI. index of 2.7.times.10.sup.-3 (kJ/mole/degree).
EXAMPLE 30
[0110] The structurally isomeric poly(isobutyl ethylene) of Example
19 is extruded in the extruder with a fishtail die at 265.degree.
to 285.degree. C. into panels. Milled-out test pieces have the
following characteristic values: tensile strength: 28 MPa,
elongation at break: 15%, modulus of tension: 1.7 GPa, modulus of
bending. 1.5 GPa. The corresponding characteristic values for the
unmodified poly(isobutyl ethylene) are 24 MPa, 15%, 1.3 GPa and 1.2
GPa.
EXAMPLE 31
[0111] In a bunker supply bin with impeller stirrer and a capacity
of 0.2 m.sup.3, 50 kg of a poly(ethyl ethylene co-methylethylene)
copolymer, with a methylethylene content of 92 mole percent, a melt
index of 1.8 g/min at 230.degree. C./21.9 N, are added
pneumatically. Glycidyl acrylate (150 g) and 135 g of
methoxybenzoyl peroxide are evaporated under vacuum by a vaporizer
and supplied to the container with the help of the circulating gas,
the modifiers being absorbed at 350.degree. K by the powdery
copolymer. The mixture is added at the rate of 24 kg/h into a
Werner & Pfleiderer ZSK 30 twin-screw extruder (L/D=42) under
inert gas, with vacuum degassing and strand granulation and having
a temperature profile of
100.degree./145.degree./175.degree./180.degree./185.degree./17-
0.degree./145.degree. C. The resulting structurally isomeric
poly(ethyl ethylene co-methylethylene) copolymer has a .PSI. index
of 4.0.times.10.sup.-3 (kJ/mole/degree) and is present in H and Y
structures, wherein R.sub.1.dbd.R.sub.3.dbd.C.sub.2H.sub.5 and
R.sub.2.dbd.R.sub.5.dbd.H, R.sub.4.dbd.CH.sub.3 and y+z=820. The
proportion of polymeric bridging elements, based on glycidyl
acrylate and determined by IR spectroscopy, is approximately 0.28%
by weight and the t/u ratio is about 0.08.
EXAMPLE 32
[0112] To a bunker supply bin of Example 31, 62 kg of a powdery
poly(ethyl ethylene) homopolymer, (T.sub.g=248.degree. K,
M.sub.w=4.times.10.sup.5) are added pneumatically. Ethylhexyl
acrylate (1.86 kg) and 0.39 kg of t-butylpertoluate are evaporated
under vacuum by a vaporizer and supplied to the container with the
help of the circulating gas, the modifiers being absorbed at
340.degree. K by the powdery polymer. The mixture is added at the
rate of 19 kg/h into a twin-screw extruder of Example 1 with a
temperature profile of
90.degree./130.degree./170.degree./175.degree./1-
80.degree./180.degree.170.degree./145.degree. C. The resulting
structurally isomeric poly(ethyl ethylene) homopolymer has a .PSI.
index of 2.6.times. 10.sup.-3 (kJ/mole/degree) and is present in H
and Y structures, wherein R.sub.1.dbd.R.sub.3.dbd.R.sub.4.dbd.
C.sub.2H.sub.5 and R.sub.2.dbd.R.sub.4.dbd.H and y+z=330 and w=660.
The proportion of polymeric bridging elements, based on ethylhexyl
acrylate, is approximately 2.75%.
EXAMPLE 33
[0113] To a bunker supply bin of Example 31, 48 kg of a powdery
poly(methyl ethylene) homopolymer, (T.sub.g=263.degree. K,
M.sub.w=6.times.10.sup.5) are added pneumatically. Allyl acrylate
(168 g) and 120 g of di-t-butyl perbenzoate are evaporated under
vacuum by a vaporizer and supplied to the container with the help
of the circulating gas, the modifiers being absorbed at 355.degree.
K by the powdery polymer. The mixture is added at the rate of 22
kg/h into a twin-screw extruder of Example 31 with a temperature
profile of
100.degree./145.degree./180.degree./185.degree./180.degree./175.degree./1-
60.degree. C. The resulting structurally isomeric poly(methyl
ethylene) homopolymer has a .PSI. index of 4.0.times.10.sup.-3
(kJ/mole/degree) and is present in H and Y structures, wherein
R.sub.1.dbd.R.sub.3.dbd.R.sub.4- .dbd.CH.sub.3 and
R.sub.2.dbd.R.sub.5.dbd.H and y+z=570. The proportion of polymeric
bridging elements, determined by IR spectroscopy and based on allyl
acrylate, is approximately 0.33%.
EXAMPLE 34
[0114] To a bunker supply bin of Example 31, 46 kg of a powdery
poly(isobutyl ethylene) homopolymer, (T.sub.g=300.degree. K,
M.sub.w=6.times.10.sup.5) are added pneumatically. Allyl methyl
maleate (267 g) and 161 g of di-t-butyl hydroperoxide are
evaporated under vacuum by a vaporizer and supplied to the
container with the help of the circulating gas, the modifiers being
absorbed at 430.degree. K by the powdery polymer. The mixture is
added at the rate of 16 kg/h into a twin-screw extruder of Example
1 with a temperature profile of
170.degree./220.degree./260.degree./265.degree./260.degree./250.degree./2-
35.degree. C. The resulting structurally isomeric poly(isobutyl
ethylene) has a .PSI. index of 3.3.times.10.sup.-3 (kJ/mole/degree)
and is present in H and Y structures, wherein
R.sub.1.dbd.R.sub.3.dbd.R.sub.4.dbd.i-C.su- b.4H.sub.9 and
R.sub.2.dbd.R.sub.5.dbd.H and y+z=205. The proportion of polymeric
bridging elements, determined by IR spectroscopy and based on allyl
methyl maleate, is approximately 0.54%.
EXAMPLE 35
[0115] To a bunker supply bin with an impeller stirrer and a
capacity of 1.0 m.sup.3, 250 kg of a powdery poly(methyl ethylene
co-ethylene) copolymer, with an ethylene content of 7% and an
M.sub.w=3.5.times.10.sup- .5, are added pneumatically.
Divinylbenzene (0.5 kg) and 0.5 kg of t-butyl perbenzoate are
evaporated under vacuum by a vaporizer and supplied to the
container with the help of the circulating gas, the modifiers being
absorbed at 400.degree. K by the powdery copolymer. The copolymer,
loaded with modifiers, is added at the rate of 45 kg/h, a 10% batch
of 2-t-butyl-4-methylphenol is added at the rate of 13 kg/h and
behenic acid is added at the rate of 35 kg/h to a Werner &
Pfleiderer ZSK 53 twin-screw extruder (L/D =36) with a supply of
inert gas, 3 conveyer-type scales, vacuum degassing and underwater
granulation and having a temperature profile of
100.degree./145.degree./180.degree./185.degree./18-
0.degree./175.degree./160.degree. C. The resulting structurally
isomeric poly(methylethylene co-ethylene) copolymer has a .PSI.
index of 4.4.times. 10.sup.-3 (kJ/mole/degree) and is present in H
and Y structures, wherein R.sub.1.dbd.R.sub.3.dbd.CH.sub.3 and
R.sub.2.dbd.R.sub.4.dbd.R.sub.5.dbd.H and y+z=350 and w=700. The
proportion of polymeric bridging elements, based on divinyl
benzene, is 0.18%
EXAMPLE 36
[0116] To a bunker supply bin of Example 35, 220 kg of a powdery
poly(isobutyl ethylene co-ethylene) copolymer, with an ethylene
content of 8 mole percent and a melt index of 0.8 g/10 min at
230.degree. C., are added. Vinyltrimethoxysilane (6.6 kg) and 1.1
kg of t-butyl pertolulate are evaporated under vacuum by a
vaporizer and supplied to the container with the help of the
circulating gas, the modifiers being absorbed at 445.degree. K by
the powdery copolymer. The copolymer, loaded with modifiers, is
added at the rate of 38 kg/h, calcium stearate is added at the rate
of 0.24 kg/h and a 10% batch of octadecyl
3(3,5-di-t-butyl-4-hydroxyphenyl) propionate and
bis-2,2,6,6-tetramethyl-- 4-piperidyl sebacate is added at the rate
of 9.5 kg/h to a Werner & Pfleiderer ZSK 53 twin-screw extruder
(L/D=36) with a supply of inert gas, 3 conveyer-type scales, vacuum
degassing and underwater granulation and having a temperature
profile of 170.degree./220.degree./260.degree./2-
65.degree./260.degree./250.degree./235.degree. C. The resulting
structurally isomeric poly(isobutyl ethylene co-ethylene) copolymer
has a .PSI. index of 3.4.times.10.sup.-3 (kJ/mole/degree) and is
present in H and Y structures, wherein
R.sub.1.dbd.R.sub.3.dbd.i-C.sub.4H.sub.9 and
R.sub.2.dbd.R.sub.5.dbd.R.sub.4.dbd.H and y+z=270. The proportion
of polymeric bridging elements, determined by IR spectroscopy and
based on vinyltrimethoxysilane, is 2.8% and the t/u ratio is
11.5.
EXAMPLE 37
[0117] Into a bunker supply bin of Example 35, 270 kg of a powdery
poly(methylethylene) homopolymer (M.sub.w=4.9.times.10.sup.5,
T.sub.g=265.degree. K), onto which a mixture of 0.2% of
1,3-propylene glycol
benzenepropionate-3,5-bis(1,1-dimethylethyl)-4-hydroxy-2,2-bis((3--
(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)-1-oxopropoxy)methyl)
and 0.1% of di-t-butylhydroxytoluene were drummed, are metered
pneumatically. Styrene (4.05 kg) and 0.81 kg of t-butylpertoluate
are evaporated under vacuum by a vaporizer and supplied to the
container with the help of the circulating gas, the modifiers being
absorbed at 385.degree. K by the powdery polymer. The powdery
mixture is added at the rate of 48 kg/h to a Werner &
Pfleiderer ZSK 53 twin-screw extruder (L/D=36) with a supply of
inert gas, vacuum degassing and underwater granulation and having a
temperature profile of
100.degree./145.degree./180.degree./185.degree./18-
0.degree./175.degree./160.degree. C. The resulting structurally
isomeric poly(methyl ethylene) has a .PSI. index of
4.2.times.10.sup.-3 (kJ/mole/degree) and is present in H and Y
structures, wherein R.sub.1.dbd.R.sub.3.dbd.R.sub.4.dbd.CH.sub.3
and R.sub.2.dbd.R.sub.5.dbd.- H and y+z=590. The proportion of
polymeric bridging elements, determined by IR spectroscopy and
based on styrene, is 1.33%.
EXAMPLE 38
[0118] The structurally isomeric poly(isobutyl ethylene) of
Examples 34 (45 parts) is mixed with 55 parts of unmodified
poly(isobutyl ethylene), 0.28 parts of
2-t-butyl-4,6-dimethylphenol, 0.15 parts of behenic acid, 0.25
parts of calcium stearate and 0.15 parts of
poly((1,1,3,3-tetramethy-
lbutyl)-imino)-1,3,5-triazine-2,4,diyl)-(2,2,6,6-tetra-methylpiperidyl)-am-
ino-hexamethylene-4-(2,2,6,6-tetrarethyl)piperidyl)-imino) and
homogenized in the extruder at
245.degree./270.degree./280.degree./280.degree./280.de-
gree./270.degree./250.degree. C. The resulting compound has a .PSI.
index of 2.75.times.10.sup.-3 (kJ/mole/degree).
EXAMPLE 39
[0119] The structural isomeric poly(alkyl ethylenes) of Examples
31, 32 and 33 (20 parts of each) are homogenized with 20 parts of
an unmodified poly(methyl ethylene co-ethylene) copolymer having an
ethylene content of 8%, 10 parts of an unmodified poly(ethyl
ethylene co-methylethylene) copolymer having an ethylene content of
15%, 9 parts of talcum and 1 part of carbon black in the extruder
at 145.degree./190.degree./230.degree./23-
0.degree./220.degree./210.degree./200.degree. C. The alloy has a
.PSI. index of 2.6.times.10.sup.-3 (kJ/mole/degree).
EXAMPLE 40
[0120] The structurally isomeric poly(isobutyl ethylene) of Example
34 is extruded in the extruder with a fishtail die at 260.degree.
to 280.degree. C. into panels. Milled-out test pieces have the
following characteristic values: tensile strength: 29 MPa,
elongation at break: 14%, modulus of tension: 1.8 GPa, modulus of
bending: 1.6 GPa. The corresponding characteristic values for the
unmodified poly(isobutyl ethylene) are 24 MPa, 15%, 1.3 GPa and 1.2
GPa.
* * * * *