Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymerizing in two or more physically distinct zones
Reexamination Certificate
1997-10-07
2001-02-13
Zitomer, Fred (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymerizing in two or more physically distinct zones
C526S067000, C528S332000, C528S335000
Reexamination Certificate
active
06187877
ABSTRACT:
The present invention relates to an improved process for preparing a polymer based on a dicarboxylic acid and a diamine by polycondensation in an extruder.
DE-A 1,720,349 describes the preparation of relatively high molecular weight polyamide-66 having a K value in the range from 69 to 72 by continuous further condensation of low molecular weight polyamide-66 having a K value in the range from 30 to 60 in a corotating screw reactor.
Disadvantages of this process are that the process is only suitable for post-condensation and that the prepolymer used has to be prepared conventionally in stirred reactors or tube reactors.
It is known that in these conventional processes, described for example in DE-A 929 151, DE-A 24 10 474, EP-A 129 195 and EP-A 129 196, aqueous solutions of the monomer compounds are used. These can be conveyed without problems as single-phase liquids through pipes and pumps. A disadvantage is that large amounts of water have to be removed with high consumption of energy before the post-condensation to higher molecular weight polymers can be carried out. In addition, conventional reactors are designed with large dimensions so as to be able to accommodate the large volume of water vapor. This results in poor space-time yields. Furthermore, the vapor to be removed is generally contaminated with monomers so that it has to be subjected to complicated purification and the monomers have to be recycled. In addition, large reactors are very unfavorable when changing products because of the large intermediate runs.
EP-A 123 377 describes a polycondensation process for preparing polyamides by feeding a heated solution of a salt or a prepolymer or a mixture thereof into a vaporization reactor to form an aerosol mist, with this vaporization reactor having a high heat flow and the polymer obtained being held therein for up to 20 seconds. However, this procedure is economically unfavorable because of, inter alia, the technical expense of generating pressures and high temperatures, the control units required and the handling of the aerosol mist. In addition, the process is, because of the high temperatures used, preferably suitable for preparing high-temaLoerature-resistant polyamides based on aromatic dicarboxylic acids and diamines.
It is an object of the present invention to provide an improved process which does not have the specified disadvantages. In particular, there is to be provided a process which starts out from solid monomers or monomer mixtures containing little water and which leads to polymers in which the difference between carboxyl end groups and amino end groups is not greater than 80, and which can be rapidly heat-treated to give polymers having high molecular weights.
We have found that this object is achieved by a process for preparing a polymer based on a dicarboxylic acid and a diamine by polycondensation in an extruder, by
(a) heating a mixture of a dicarboxylic acid having from 4 to 12 carbon atoms and a diamine having from 4 to 12 carbon atoms, which mixture is solid at room temperature and has a residual moisture content of less than 5% by weight, to a temperature in the range from 150 to 400° C. under autogenous pressure in a contrarotating twin-screw extruder to give a product A,
(b) feeding the product A to a corotating twin-screw extruder, with the product A being exposed to a temperature in the range from 150 to 400° C. and residual water present and also water from the polycondensation being removed through the degassing openings, to give a product B, with the proviso that the corotating twin-screw extruder has at least two segments having different pressures.
The starting materials used according to the invention are mixtures of a dicarboxylic acid having from 4 to 12 carbon atoms and a diamine having from 4 to 12 carbon atoms, preferably equimolar mixtures having an excess of one component of less than 5 mol %, preferably less than 2 mol %, particularly preferably less than 1 mol %.
Dicarboxylic acids used are preferably adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid and also terephthalic acid, isophthalic acid, 5-sulfoisophthalic acid or mixtures of the specified dicarboxylic acids, particularly preferably adipic acid.
Diamines used are preferably tetramethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine and dodecamethylenediamine and also m-xylylenediamine, bis(4-aminophenyl)methane, 2,2-bis(4-aminophenyl)propane and bis(4-aminocyclohexyl)methane, or mixtures of the specified diamines, particularly preferably hexamethylenediamine.
In a preferred embodiment, hexamethylenediammonium adipate (“AH salt”) is used.
According to the invention, the residual moisture content of the mixture used is less than 5, preferably less than 2, particularly preferably less than 1.5, % by weight.
According to the invention, a monomer mixture as above is fed to a contrarotating twin-screw extruder in which the monomer mixture is melted. The screws of the contrarotating twin-screw extruder preferably have a length: diameter ratio of from 12 to 50, particularly preferably from 18 to 36. In a particularly preferred embodiment, the screw diameter is selected in the range from 25 to 250 mm, in particular from 40 to 130 mm.
It is further preferred that the contrarotating twin-screw extruder is divided into segments with separately adjustable temperatures, of which the first segment having a length of from 4 to 8 D is preferably set to a temperature from 20 to 180° C., particularly preferably from 25 to 100° C., below the melting point of the polyamide formed. For the subsequent segments, the temperatures selected are preferably from 5° C. below and 50° C. above, in particular from 5 to 50° C. above, the melting point of the polyamide formed. In a particularly preferred embodiment for preparing polyamide 66, the temperature range for the subsequent segments is from 250 to 300° C., in particular from 260 to 300° C., more particularly from 260 to 275° C.
Furthermore, the rotation rate selected is usually in the range from 50 to 250 rpm, preferably from 100 to 200 rpm.
It is essential to the invention that in the contrarotating twin-screw extruder there prevails an autogenous pressure which is determined by the selected temperature and the volatility of the components (monomers, water of reaction and any residual moisture in the monomer mixture). This can be achieved by selecting the spacing between extruder screw and internal wall of the barrel so that the relative gap G=(D−D
B
)/D, where D=2×radius of the extruder screw at the flight and D
B
=2×internal radius of the barrel, is usually less than 0.02, preferably in the range from 0.015 to 0.0001, particularly preferably in the range from 0.006 to 0.001. In a particularly preferred embodiment having a D of 34 mm, the spacing (D−D
B
) is selected so as to be <0.5 mm, preferably <0.2 mm, which corresponds to values of G<0.015 preferably G<0.006.
Furthermore, the rotation rate selected is usually in the range from 50 to 250 rpm, preferably from 100 to 200 rpm.
The residence time in the contrarotating extruder is usually selected so as to be in the range from 0.5 to 8 min, preferably from 1 to 4 min.
According to the invention, the (molten) product A and the associated gases (water vapor and monomer vapors) from the contrarotating twin-screw extruder are fed to a corotating twin screw extruder. The polycondensation is advantageously carried out at liquid-phase temperatures in the range from 150 to 400° C., preferably from 180 to 300° C., but above the melting point of the polymer to be prepared. For example, in the preparation of polyamide-66, the temperature is selected so as to be in the range from 255 to 300° C., particularly preferably from 260 to 285° C.
The corotating (based on the direction of rotation of the extruder screws) twin-screw extruder usually has a length: diameter ratio (L:D) in the range from 12 to 50, preferably from 18 to 36. In a particularly preferred embodiment, the screw diameter is selec
Gotz Walter
Hofmann Jurgen
Horle Helmut
Kopietz Michael
BASF - Aktiengesellschaft
Keil & Weinkauf
Zitomer Fred
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