Method for the continuous production of biodegradable polyesters
A process for the continuous production of a biodegradable polyester, where a mixture of aliphatic dihydroxy compounds, aliphatic and aromatic dicarboxylic acids or their liquid esters, and, optionally, further comonomers is mixed, without addition of a catalyst, to give a paste, and i) this mixture with at least a portion of the catalyst, is continuously esterified or, transesterified; ii) the transesterification or, esterification product obtained in i) is continuously precondensed with any remaining amount of catalyst to an intrinsic viscosity of from 20 to 70 cm 3 /g; iii) the product obtainable from ii) is continuously polycondensed to an intrinsic viscosity of from 60 to 170 cm 3 /g, and iv) the product obtainable from iii) is reacted continuously with a chain extender in a polyaddition reaction to an intrinsic viscosity of from 150 to 320 cm 3 /g. The invention further relates to biodegradable polyesters obtained by this process.
1. A process for the continuous production of a biodegradable polyester based on aliphatic or aliphatic and aromatic dicarboxylic acids and on aliphatic dihydroxy compounds, where
a mixture composed of the aliphatic dihydroxy compounds, of the aliphatic and aromatic dicarboxylic acids, and, optionally, of further comonomers (component C) is mixed, without addition of a catalyst, to give a paste, or, as an alternative, the liquid esters of the dicarboxylic acids are fed into the system, as also are the dihydroxy compound and, optionally, further comonomers, without addition of any catalyst, where
i) in a first stage, this mixture, together with the entire amount or with a portion of the catalyst, is continuously esterified or, respectively, transesterified;
ii) in a second stage, the transesterification or, respectively, esterification product obtained in i) is continuously precondensed to an intrinsic viscosity of from 20 to 70 cm 3 /g to DIN 53728;
iii) in a third stage, the product obtainable from ii) is continuously polycondensed to an intrinsic viscosity of from 60 to 170 cm 3 /g to DIN 53728, and
iv) in a fourth stage, the product obtainable from iii) is reacted continuously with a chain extender D in a polyaddition reaction to an intrinsic viscosity of from 150 to 320 cm 3 /g to DIN 53728;
where stage ii) is carried out in a tower reactor, and the product stream is conducted concurrently by way of a falling-film cascade, and the reaction vapors are removed in situ from the reaction mixture.
2. The process according to claim 1 , where the biodegradable polyester is composed of:
A) an acid component composed of
a1) from 30 to 99 mol % of at least one aliphatic dicarboxylic acid or its esters, or a mixture thereof,
a2) from 1 to 70 mol % of at least one aromatic dicarboxylic acid or its esters, or a mixture thereof, and
a3) from 0 to 5 mol % of a compound comprising sulfonate groups,
where the total of the molar percentages of components a1) to a3) is 100%, and
B) a diol component composed of:
b1) at least equimolar amounts with respect to component A of a C 2 -C 12 alkanediol, or a mixture thereof, and
b2) from 0 to 2% by weight, based on components A and b1), of a compound comprising at least 3 functional groups;
and, optionally, one or more components selected from
C) a component selected from
c1) at least one dihydroxy compound comprising ether functions and having the formula I
HO—[(CH 2 ) n —O] m —H (I)
where n is 2, 3 or 4 and m is a whole number from 2 to 250,
c2) at least one hydroxycarboxylic acid of the formula IIa or IIb
where p is a whole number from 1 to 1500 and r is a whole number from 1 to 4, and G is a radical selected from the group consisting of phenylene, —(CH 2 ) q —, where q is a whole number from 1 to 5, —C(R)H— and —C(R)HCH 2 , where R is methyl or ethyl,
c3) at least one amino-C 2 -C 12 alkanol, or at least one amino-C 5 -C 10 cycloalkanol, or a mixture of these,
c4) at least one diamino-C 1 -C 8 alkane,
c5) at least one aminocarboxylic acid compound selected from the group consisting of caprolactam, 1,6-aminocaproic acid, laurolactam, 1,12-aminolauric acid, and 1,11-aminoundecanoic acid,
or mixtures composed of c1) bis c5),
and
D) from 0.01 to 4% by weight, based on the amount of polyester after stage iii, of at least one component selected from the group d1) to d4)
d1) of a di- or oligofunctional isocyanate and/or isocyanurate,
d2) of a di- or oligofunctional peroxide,
d3) of a di- or oligofunctional epoxide,
d4) of a di- or oligofunctional oxazoline, oxazine, caprolactam, and/or carbodiimide;
E) from 0 to 10% by weight, based on the amount of polyester after stage iii of a component selected from the group e1) to e3)
e1) of a lubricant,
e2) of a nucleating agent,
e3) of an aliphatic polyester selected from the group consisting of: polylactic acid, polycaprolactone, polyhydroxyalkanoate.
3. The process according to claim 1 , where the biodegradable polyester comprises, as aliphatic dicarboxylic acid (component a1)), succinic acid, adipic acid, or sebacic acid, esters thereof, or a mixture of these;
as aromatic dicarboxylic acid (component a2)), terephthalic acid or its esters;
as diol component (component B), 1,4-butanediol or 1,3-propanediol,
as component b2) glycerol, pentaerythritol, trimethylolpropane, and,
as component d1), hexamethylene diisocyanate.
4. The process according to claim 1 , where the esterification/transesterification (stage i)) uses a hydrocyclone with attached heat exchange, and stage i), ii), and iii) is carried out in the presence of a titanium catalyst.
5. The process according to claim 1 , where, in stage ii), the transesterification product or esterification product is precondensed to an intrinsic viscosity of from 25 to 55 cm 3 /g to DIN 53728.
6. The process according to claim 1 , where, between stage ii) and iii), from 0.001 to 0.1% by weight of a deactivating phosphorus compound, or from 0.001 to 1.5% by weight of a color-stabilizing or activating phosphorus compound, is added to the product stream.
7. The process according to claim 1 , where, at the start of, during, or at the end of stage iii, or in an upstream step iva of the chain-extension process ivb, from 0.01 to 2.0% by weight, based on the respective polymer composition, of an acid scavenger selected from the group of a di- or oligofunctional epoxide (d3), oxazoline, oxazine, caprolactam, and/or carbodiimide (d4) is added.
8. The process according to claim 1 , where stage iii) is carried out in a rotating-disk reactor or cage reactor.
9. The process according to claim 1 , where, after stage iii), from 0.05 to 2.0% by weight, based on the polymer composition after stage iii, of a lubricant e1 is added.
10. The process according to claim 1 , where, after stage iii), from 0.05 to 5.0% by weight, based on the polymer composition after stage iii, of a nucleating agent e2 is added.
11. The process according to claim 1 , where, after stage iii), from 0.05 to 15.0% by weight, based on the polymer composition after stage iii, of a compatibilizer e3 is added.
12. The process according to claim 1 , where stage iv) is carried out in an extruder, List reactor, or static mixer.
13. The process according to claim 12 , where, in stage iv), hexamethylene diisocyanate (component d1) is used as chain extender.
14. The process according to claim 2 , wherein the lubricant is erucamide or a stearate.
15. The process according to claim 2 , wherein the nucleating agent is calcium carbonate, polyethylene terephthalate, or polybutylene terephthalate.
16. The process according to claim 1 , wherein the biodegradable polyester has an acid number, measured to DIN EN 12634, which is smaller than 1.0 mg KOH/g.