阅读说明：本技术 玻璃纤维增强的tpu (Glass fiber reinforced TPU ) 是由 O·S·赫兹 T·朗格 B·尼茨 于 2019-07-11 设计创作，主要内容包括：本发明涉及包含热塑性聚氨酯(TPU-1)和填料(F1)的组合物,所述热塑性聚氨酯(TPU-1)通过使多异氰酸酯组合物(IZ)与多元醇组合物(PZ)反应获得或可获得,所述多元醇组合物(PZ)包含至少多元醇(P1)、扩链剂(KV1)和扩链剂(KV2)。本发明也涉及一种制备这类组合物的方法。本发明还涉及本发明的组合物用于制备成型产品的用途以及包含本发明的组合物的成型产品。(The invention relates to a composition comprising a thermoplastic polyurethane (TPU-1) and a filler (F1), said thermoplastic polyurethane (TPU-1) being obtained or obtainable by reacting a polyisocyanate composition (IZ) with a polyol composition (PZ) comprising at least a polyol (P1), a chain extender (KV1) and a chain extender (KV 2). The invention also relates to a method for preparing such a composition. The invention also relates to the use of the composition according to the invention for producing shaped products and to shaped products comprising the composition according to the invention.)

1. A composition comprising:

(a) a thermoplastic polyurethane (TPU-1) obtained or obtainable by reacting a polyisocyanate composition (IZ) with a polyol composition (PZ),

wherein the polyol composition (PZ) comprises at least one polyol (P1), a chain extender (KV1) and a chain extender (KV2), wherein the chain extender is used in a molar mixing ratio of 20:1 to 3:1 KV1: KV 2; and

(b) a filler (F1).

2. The composition according to claim 1, wherein the chain extender (KV1) and/or chain extender (KV2) is selected from 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol and 1, 6-hexanediol, diethylene glycol, triethylene glycol, hydroquinone bis-2-hydroxyethyl ether and bis (2-hydroxyethyl) terephthalate.

3. The composition according to claim 1 or 2, wherein the chain extender (KV1) is 1, 4-butanediol.

4. The composition according to any one of claims 1 to 3, wherein the polyol (P1) is a polyether polyol.

5. The composition according to any one of claims 1 to 4, wherein the polyisocyanate composition (IZ) comprises a polyisocyanate (P1) selected from: phenylene 1, 2-diisocyanate, phenylene 1, 3-diisocyanate and/or phenylene 1, 4-diisocyanate; triphenylmethane 4, 4', 4 "-triisocyanate; naphthylene 1, 5-diisocyanate (NDI); benzylidene 2, 4-diisocyanate and/or benzylidene 2, 6-diisocyanate (TDI); biphenyl 2,4 '-diisocyanate, biphenyl 4, 4' -diisocyanate and/or biphenyl 2, 2-diisocyanate; diphenylmethane 2,2 ' -diisocyanate, diphenylmethane 2,4 ' -diisocyanate and/or diphenylmethane 4,4 ' -diisocyanate (MDI); polyphenyl polymethylene polyisocyanates; xylylene 1, 2-diisocyanate, xylylene 1, 3-diisocyanate and/or xylylene 1, 4-diisocyanate and m-tetramethylxylylene diisocyanate (TMXDI).

6. The composition according to any one of claims 1 to 5, wherein the filler (F1) is a fiber.

7. The composition according to any one of claims 1 to 6, wherein the filler (F1) is selected from glass fibers, carbon fibers, polyaramide fibers, potassium titanate fibers, fibers composed of liquid crystalline polymers, metal fibers, polyester fibers, polyamide fibers, organic fibrous fillers and inorganic fibrous fillers.

8. The composition according to any one of claims 1 to 7, wherein the filler (F1) has a length of 3mm to 4mm and a diameter of 1 μm to 20 μm, in each case determined according to ASTM D578-98.

9. The composition according to any one of claims 1 to 8, wherein the filler (F1) is present in an amount of from 40 to 60% by weight, based on the total composition.

10. The composition according to any one of claims 1 to 9, wherein the thermoplastic polyurethane has a shore hardness of from 40D to 90D, preferably from 70D to 90D, as determined according to DINISO 7619-1.

11. A method of making a composition comprising the steps of:

(i) mixing the following components:

(a) a thermoplastic polyurethane (TPU-1) obtained or obtainable by reacting a polyisocyanate composition (IZ) and a polyol composition (PZ),

wherein the polyol composition (PZ) comprises at least one polyol (P1), a chain extender (KV1) and a chain extender (KV2), wherein the chain extender is used in a molar mixing ratio of 20:1 to 3:1 KV1: KV 2; and

(b) a filler (F1).

12. A composition obtained or obtainable by the process according to claim 11.

13. Use of a composition according to any one of claims 1 to 10 or obtained or obtainable by the process according to claim 11 for the preparation of shaped bodies.

14. Shaped body comprising a composition according to any one of claims 1 to 10 or obtained or obtainable by a process according to claim 11.

2. Preparation examples

2.1 preparation by hand casting (TPU 1-3)

The polyol and chain extender amounts specified in the base formulation (table 1) were weighed into tin cans and briefly blanketed with nitrogen. The can was closed with a lid and heated in an oven to about 90 ℃.

Another oven for heat treating the polyurethane sheet was preheated to 80 ℃. A teflon plate was placed on the hot plate and set to 125 ℃.

The calculated amount of liquid isocyanate was determined by volume measurement. For this purpose, the liquid isocyanate (volume of MDI measured at a temperature of about 48 ℃) was weighed into a PE beaker and poured into the PE beaker within 10 s. The tare weight of the beaker emptied in this way was then determined and the calculated amount of isocyanate was added. In the case of MDI, it is stored in an oven at about 48 ℃.

Additives present in solid form at room temperature, such as hydrolysis protectors, antioxidants, etc., are weighed directly.

The preheated polyol is placed on a lift table below the static mixer. The reaction vessel is then lifted by the lift table until the stirrer blades are fully immersed in the polyol.

Before starting the agitator motor, it must be ensured that the speed regulator is in the zero position. The speed of rotation is then increased slowly to ensure good mixing without stirring the air.

Additives (e.g., antioxidants) are then added to the polyol.

The temperature of the reaction mixture was carefully set to 80 ℃ by a hot air blower.

If desired, the catalyst is metered into the reaction mixture by means of a microsyringe before the isocyanate is added. The addition of the isocyanate was then carried out by introducing the previously measured amount by volume of isocyanate into the reaction mixture over a period of 10s at 80 ℃. The weight was monitored by weighing. Deviations from the formula amounts of greater/less than 0.2g are recorded. A stopwatch was started when the isocyanate was added. When the temperature reached 110 ℃, the reaction mixture was poured into teflon plates that had been preheated to 125 ℃.

10 minutes after the start of the stopwatch, the polyurethane sheet was removed from the hot plate and stored in an oven at 80 ℃ for 15 hours. The cooled polyurethane chips were comminuted in a chopper. The granular material was then dried at 110 ℃ for 3 hours and stored dry.

The process can in principle be transferred to a reaction extruder or a belt process.

Table 1: formula of TPU 1-3

	TPU 1	TPU 2	TPU 3
				PTHF 1000[g]	393.2	100	100
Lupranat MET[g]	471.8	395.5	395.5
				1, 4-butanediol [ g ]]	135.0	133.4	121.7
1, 3-propanediol [ g ]]	-	-	9.8

Table 2: properties of TPU1 to 3

2.2 preparation of TPU 4-6

Table 3 below shows the compositions in which the raw materials are reported in parts by weight (pbw). The mixtures were prepared in each case using a twin-screw extruder, type ZE 40A, from Berstorff, with a processing part length 35D divided into 10 barrel segments. Continuous granulation was used.

Table 3: formula of TPU 1-3

Table 4: properties of TPU 4-6

3. Results

TPU 2 cannot be processed. This material has a very high melting range and does not allow the preparation of glass fiber composites.

TPU 4 is preparable, but the E modulus is only 4080 MPa.

Surprisingly, TPU 6 is preparable. The E modulus was 18300 MPa.

4. Measurement method

Shore hardness A DIN ISO 7619-1, Shore hardness test A (3s)

Tensile Strength DIN EN ISO 527

Elongation at break DIN EN ISO 527

Propagation tear resistance: DIN ISO 34-1, B (B)

The citation of documents

Kunststoffhandbuch, Vol.VII, by Vieweg andediting, Carl Hanser Verlag, Munich 1966 (page 103-113)

EP 0 922 552 A1

DE 101 03 424 A1

WO 2006/072461 A1