Structural isomers of poly (alkyl ethylenes)

Details Structural isomers of poly (alkyl ethylenes) Structural isomers of poly (alkyl ethylenes)

1997-01-27

2002-05-14

Mullis, Jeffrey (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Mixing of two or more solid polymers; mixing of solid...

C525S267000, C525S273000, C525S307000, C525S311000, C525S313000, C525S319000, C525S320000

Reexamination Certificate

active

06388020

ABSTRACT:

BACKGROUND OF THE INVENTION
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.
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).
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(ethylene 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).
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).
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) (Rätzsch, M., Angew. Makromol. Chemie 229 (1995), 145-158).
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.
SUMMARY OF THE INVENTION
The invention is 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 ethylene) with an H and a Y structure.
DETAILED DESCRIPTION OF THE INVENTION
The poly (alkyl ethylenes) of the present invention and a process for making the same are described herein.
The &psgr; index has proven to be a suitable criterion for characterizing the processing behavior of poly(alkyl ethylenes):
&psgr;=Tm×&Dgr;Hm×&bgr;×&xgr;×Tg
−1
(kJ/mole/degree)
in which
Tm=melting temperature (°K.)
&Dgr;Hm=heat of fusion (kJ/mole)
&bgr;=coefficient of linear thermal expansion at 25° C. (1/degree)
&xgr;=threshold value
Tg=glass transition temperature (°K.)
The melting temperature (Tm(°K.) and heat of fusion DHm (kJ/mole) are determined according to the methods of the DIN 51004 or ISO 3146. The coefficient of linear thermal expansion b (1/degree) at 24° C. is determined according to the method of DIN 53752. The threshold value x is determined by the MFI determination according to the method of the ISO 1131 by determining the strand diameter of the structurally isomeric polyalkylethylene d
I
(mm) produced, as well as the strand diameter of the unmodified polyalkylethylene starting material d
A
(mm) and forming the ratio d
I
/d
A
. The glass transition temperature is determined by the method of DIN 61006.
For the starting materials (unmodified polyalkylethylene), the melting temperature, glass transition temperature, heat of fusion and coefficient of linear thermal expansion &bgr; 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).
Pursuant to the invention, the poly(alkyl ethylenes), with an H and a Y structure and a &psgr; index of 2×10
−3
to 8×10
−3
(kJ/mole/degree), have significantly more advantageous processing properties than do unmodified poly(alkyl ethylenes). For example the &psgr; value is of the order of 1.88×10
−3
(kJ/mole/degree) for poly(isobutyl ether) and 1.84×10
−3
(kJ/mole/degree) for poly (ethyl ethylene).
Poly(alkyl ethylenes) with an H structure are macromers of the structure
wherein
R
1
=C
1
to C
4
alkyl, R
2
=H, t/u=0.03 to 30, R
3
=C
1
to C
4
alkyl or H, R
4
=H, C
1
to C
4
alkyl, halogen or aryl, particularly phenyl, R
5
=H or C
1
to C
4
alkyl and y+z=150 to 3,000.
&Xgr;=polymeric bridging segments comprising acrylic acid, C
4
to C
12
acrylic acid derivatives, C
3
to C
21
allyl compounds, C
8
to C
14
diacrylates, C
7
to C
16
diallyl compounds, C
4
to C
10
dienes, C
9
to C
15
dimethacrylates, C
7
to C
10
divinyl compounds, C
3
to C
16
monovinyl compounds, C
12
to C
17
polyacrylates, C
15
to C
21
polymethacrylates, C
9
to C
12
triallyl compounds and/or macromers comprising oligobutadienes, polysiloxanes and/or polyethers.
Poly(alkyl ethylenes) with a Y structure are macromers having the structure
in which R=C
1
to C
4
alkyl, R
2
=H, R
3
=C
1
to C
4
alkyl or H, R
4
=H, C
1
to C
4
alkyl, halogen or aryl, particularly phenyl, R
5
=H or C
1
to C
4
alkyl, y+z=150 to 3,000, t/u=0.03 to 30 and w=250 to 5,000.
&Xgr;=polymeric bridging segments based on acrylic acid, C
4
to C
12
acrylic acid derivatives, C
3
to C
21
allyl compounds, C
8
to C
14
diacrylates, C
7
to C
16
diallyl compounds, C
4
to C
10
dienes, C
9
to C
15
dimethacrylates, C
7
to C
10
divinyl compounds, C
3
to C
16
monovinyl compounds, C
12
to C
17
polyacrylates, C
15
to C
21
polymethacrylates, C
9
to C
12
triallyl compounds and/or macromers based on oligobutadienes, polysiloxanes and/or polyethers.
The proportion of polymeric bridging elements in the poly(alkyl ethylenes) with H and Y structures is 0.1 to 5% by weight.
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.
Poly(alkyl ethylenes) with an H and a Y structure are preferred, in which R
1
and R
3
are formed by ethyl, methyl or isobutyl groups, R
2
and R
5
are formed by H and R
4
is formed by ethyl, n-butyl, methyl or isobutyl groups or by H or Cl.
Mixtures of these structurally isomeric poly(alkyl ethylenes) also have these inventive properties. Preferred &psgr; values lie between 2.5×10
−3
and 6×10
−3
(kJ/mole/degree).
Suitable monovinyl compounds for the bridging segments &Xgr; are p-acetoxystyr

Affiliated with

Also associated with

Rating

Structural isomers of poly (alkyl ethylenes) does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Structural isomers of poly (alkyl ethylenes), we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Structural isomers of poly (alkyl ethylenes) will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2901942