阅读说明：本技术 脂族热塑性聚氨酯及其制备和用途 (aliphatic thermoplastic polyurethanes, their preparation and use ) 是由 C.旺普雷希特 C.伊尔勒 于 2018-04-18 设计创作，主要内容包括：本发明涉及具有改善的起霜行为、良好的耐热性和快速的工业可加工性的脂族的、耐光照的热塑性聚氨酯及其制备和用途。(the invention relates to aliphatic, light-resistant thermoplastic polyurethanes having improved blooming behavior, good heat resistance and rapid industrial processability, to the production and use thereof.)

1. Aliphatic, light-stable thermoplastic polyurethanes which may be prepared from

A) An isocyanate component consisting of

a1) 100 to 70mol% of 1, 10-diisocyanatodecane and/or 1, 12-diisocyanatododecane,

a2) 0 to 30 mol% of one or more aliphatic, cycloaliphatic and/or aromatic diisocyanates other than 1, 10-diisocyanatodecane and 1, 12-diisocyanatododecane,

B) At least one polyol component selected from the group consisting of: polyester polyols, polyether polyols, polycarbonate polyols, polyether carbonate polyols, the number-average molecular weights of each of which are 500-8000 g/mol,

C) At least one chain extender component selected from the group consisting of: ethylene glycol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 2-dodecanediol, 1, 4-cyclohexanediol, bis- (hydroxymethyl) -cyclohexane, 1, 4-bis (hydroxyethyl) -hydroquinone, neopentyl glycol, 1, 4-butenediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, terephthalic acid-bis-ethylene glycol, terephthalic acid-bis-1, 3-propanediol, terephthalic acid-bis-1, 4-butanediol, ethoxylated bisphenol, ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, N-methylpropylenediamine, N' -dimethyl-ethylenediamine, isophoronediamine, 2, 4-tolylenediamine, 2, 6-tolylenediamine, 3, 5-diethyl-2, 4-tolylenediamine, 3, 5-diethyl-2, 6-tolylenediamine, 2-hydroxyethylamine,

D) optionally monofunctional chain terminators

Obtained in the presence of

E) optionally a catalyst, which is added to the reaction mixture,

F)0.05 to 5 wt.%, based on the thermoplastic polyurethane, of an oxidation and/or light stabilizer,

G) optionally further additives and/or auxiliaries,

wherein the ratio of isocyanate groups from A) to groups reactive toward isocyanate groups from B), C) and D) is from 0.9:1 to 1.1: 1.

2. The aliphatic, light-resistant thermoplastic polyurethane according to claim 1,

The isocyanate component A) consists of

a1) 100 to 70mol% of 1, 10-diisocyanatodecane and/or 1, 12-diisocyanatododecane,

a2) 0 to 30 mol% of one or more aliphatic and/or cycloaliphatic diisocyanates other than 1, 10-diisocyanatodecane and 1, 12-diisocyanatododecane.

3. the aliphatic, light-resistant thermoplastic polyurethane according to claim 1,

the isocyanate component A) consists of

a1) 100 to 70mol% of 1, 10-diisocyanatodecane and/or 1, 12-diisocyanatododecane,

a2) 0 to 30 mol% of one or more aliphatic diisocyanates other than 1, 10-diisocyanatodecane and 1, 12-diisocyanatododecane.

4. The aliphatic, light-resistant thermoplastic polyurethane according to claim 1,

The isocyanate component A) consists of

a1) 100 to 70mol% of 1, 10-diisocyanatodecane and/or 1, 12-diisocyanatododecane,

a2) 0 to 30 mol% of 1, 6-diisocyanatohexane.

5. The aliphatic, light-resistant thermoplastic polyurethane according to claim 1,

The polyols of component B) each have a number average molecular weight of 750-6000 g/mol.

6. The aliphatic, light-resistant thermoplastic polyurethane according to claim 1,

The polyols of component B) each have a number average molecular weight of 900-4200 g/mol.

7. the aliphatic, light-resistant thermoplastic polyurethane according to claim 1,

one or more chain extenders selected from the group consisting of: ethylene glycol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 2-dodecanediol, 1, 4-cyclohexanediol, bis- (hydroxymethyl) -cyclohexane, 1, 4-bis (hydroxyethyl) -hydroquinone, neopentyl glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, terephthalic acid-bis-ethylene glycol, ethylenediamine, isophoronediamine, 2, 4-toluenediamine and 2-hydroxyethylamine.

8. The aliphatic, light-resistant thermoplastic polyurethane according to claim 1,

One or more chain extenders selected from the group consisting of: ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, and 1, 4-di- (hydroxyethyl) -hydroquinone.

9. Process for the continuous preparation of aliphatic, light-resistant thermoplastic polyurethanes according to one or more of claims 1 to 8,

i) The polyol component B) and the chain extender component C) are mixed continuously,

ii) reacting the mixture from step i) with an isocyanate component A),

iii) allowing the reaction to proceed to completion in a discharge vessel, and

Optionally, the product is granulated and then,

wherein the addition of component F) can be carried out at any point in steps i) and ii).

10. Process for the continuous preparation of aliphatic, light-resistant thermoplastic polyurethanes according to one or more of claims 1 to 8,

i) The isocyanate component A) and the polyol component B) are continuously mixed and reacted,

ii) reacting the resulting reaction product from step i) with a chain extender component C),

iii) allowing the reaction to proceed to completion in a discharge vessel, and

Optionally, the product is granulated and then,

wherein the addition of component F) can be carried out at any point in steps i) and ii).

11. Use of the aliphatic, light-resistant thermoplastic polyurethane according to claims 1 to 8 for producing extrudates and injection-molded parts.

12. use of the aliphatic, light-resistant thermoplastic polyurethanes according to claims 1 to 8 as sinterable powders for the production of flat structures and hollow bodies.

13. shaped body, film or foil obtainable from the thermoplastic polyurethane according to any of claims 1 to 8.

14. Sintering powder obtainable from the thermoplastic polyurethane according to any of claims 1 to 8.

example (b):

abbreviations used hereinafter:

PE 225B: polybutylene adipate with an OH number of 50 mg KOH/g

Acclaim 2220N: polyethers having an OH number of 50 mg KOH/g (C3/C2 Mixed Ether)

desmophen C2201: polycarbonate diol having an OH number of 56 mg KOH/g

HDI: 1, 6-diisocyanatohexane

HDO: 1, 6-hexanediol

DDI: 1, 10-diisocyanato decane

t2000: polytetrahydrofuran with an OH number of 56 mg KOH/g

irganox 245: antioxidants of BASF SE

tinuvin ^ 234: benzotriazole-based light stabilizers of BASF SE

Stabaxol P200: hydrolysis protective agent for Rhein Chemie GmbH

DBTL: dibutyltin dilaurate.

General description of the preparation of TPUs:

A mixture of the respective polyol or polyol mixture (in the case of PE225B, to which polyol 1 weight percent Stabaxol P200), HDO, Irganox 245 (0.5 weight percent) based on TPU, Tinuvin 234 (0.2 weight percent based on TPU) and 80 ppm DBTL (based on polyol) was also added 3 hours before the start of the experiment) was heated to 120 ℃ with stirring. The respective diisocyanate was then added. Subsequently stirring until the maximum possible viscosity increase, and then casting the TPU into TPU casting plates. The plates were then thermally post-treated at 80 ℃ for 30 minutes. They were then cooled to room temperature. The molar composition of the TPUs prepared is shown in Table 1.

Table 1: molar composition of the prepared TPU

Not according to the invention.

The resulting TPU cast plaques are cut and granulated. The pellets were processed into bars (mould temperature: 40 ℃ C.; bar size: 80X 10X 4 mm) or slabs (mould temperature: 40 ℃ C.; size: 125X 50X 2 mm) using an injection molding machine of the type Arburg Allrounder470S at an injection flow of 10-35 cm3/S in the temperature range from 180 ℃ to 230 ℃ and in the pressure range from 650-750 bar.

melt flow index (MVR) and mechanical values (100% modulus, 300% modulus, crack resistance strength, elongation at break and shore a hardness), cure speed, abrasion and blooming behavior were determined from the prepared TPU product.

the test conditions are as follows:

1) Melt flow index (MVR):

MVR measurements were measured at 170 ℃ (example 1 + 2) and 200 ℃ (example 3 + 4) with a load bearing of 10 kg (98N) and a 5 minute warm-up time, according to ISO1133, with MVR equipment from the company fostert, model MP-D.

2) tensile test:

the tensile tests were carried out on S1 bars (corresponding to specimen type 5 according to EN ISO 527, punched out from injection plates) according to DIN53455 at a tensile speed of 200 mm/min.

3) Hardness:

The hardness measurements were carried out in accordance with DIN 53505.

4) curing speed:

In order to determine the solidification rate, the hardness development of the round shaped bodies (diameter 30 mm, height 6 mm) was measured after processing by injection molding (setting of the injection molding machine: 25 s cooling time and 25 s post-pressure time). The hardness of the test specimens was measured in accordance with DIN 53505 immediately after (0 s), 60 s and 300 s after removal from the mold.

5) Abrasion:

The abrasion was measured in accordance with DIN ISO 4649.

6) blooming behavior:

Blooming behavior was determined on injection plates. For this purpose, the panels were stored under various conditions (at 25 ℃ in ambient air; under water at 45 ℃ and at 60 ℃/90% air humidity in an air-conditioning cabinet). After a storage time of 4 weeks, the test panels were evaluated visually.

The melt flow index (MVR) and tensile test (mechanical) measurements are shown in table 2 below.

Table 2:

Not according to the invention.

The curing speed and abrasion measurements are shown in table 3 below.

Table 3:

Not according to the invention.

blooming behaviour was determined in examples 1 and 2. Visual evaluation is shown in table 4 below.

Table 4:

TPU from	Air at 25 DEG C	45 ℃ underwater	60 deg.C/90% air humidity
				Example 1	Without coating	Slight blooming	Slight blooming
Example 2	without coating	A plurality of white coating layers	a plurality of white coating layers

Not according to the invention.