阅读说明：本技术 具有改善性质的复合元件 (Composite element with improved properties ) 是由 C·格瑞尔瑟-施米茨 A·卡姆 于 2019-01-25 设计创作，主要内容包括：本发明涉及一种复合元件,该复合元件具有以下层结构：2mm至20mm的金属,10mm至100mm的致密聚氨酯制剂及另外的2mm至20mm的金属。所述聚氨酯制剂通过使(a)具有至少两个异氰酸酯基的化合物与(b)聚醚多元醇反应而获得,且该聚醚多元醇(b)为至少包含聚醚多元醇(b1)和聚醚多元醇(b2)的成分的混合物。本发明还涉及所述复合元件的用途及相关的方法。(The invention relates to a composite element having the following layer structure: 2mm to 20mm metal, 10mm to 100mm dense polyurethane formulation and a further 2mm to 20mm metal. The polyurethane formulation is obtained by reacting (a) a compound having at least two isocyanate groups with (b) a polyether polyol, and the polyether polyol (b) is a mixture of ingredients comprising at least polyether polyol (b1) and polyether polyol (b 2). The invention also relates to the use of said composite element and to the associated method.)

1. A composite element having the following layer structure:

(i)2mm to 20mm of a metal,

(ii)10mm to 100mm of a compact polyurethane formulation obtainable by reacting

(a) A compound having at least two isocyanate groups, with

(b) A polyether polyol,

optionally in the presence of

(c) Catalyst and/or

(d) An auxiliary agent and/or an additive agent,

(e) a chain extender which is a mixture of a chain extender,

(iii)2mm to 20mm of a metal,

wherein the compound a) containing isocyanate groups has an NCO content of 20 to 50%, and

the polyether polyol (b) is a mixture of ingredients including at least polyether polyol (b1) and polyether polyol (b 2).

2. The composite element according to the preceding claim, wherein the polyether polyol (b1) is present in the mixture in an amount of from 50 to 95 wt. -%, preferably from 55 to 90 wt. -%, more preferably from 60 to 85 wt. -%.

3. The composite element according to any of the preceding claims, wherein the polyether polyol (b1) has an average functionality of from 1.70 to 2.90, preferably from 1.95 to 2.8, more preferably from 2.2 to 2.7, even more preferably from 2.4 to 2.6.

4. The composite element according to any of the preceding claims, wherein the polyether polyol (b1) has a number average molecular weight of 3.0x 10³g/mol to 7.0x10³g/mol, preferably between 4.0X 10³g/mol to 6.0x10³g/mol.

5. The composite member of any preceding claim, wherein polyether polyol (b2) is present in the mixture in an amount of from 5 wt% to 50 wt%.

6. The composite element according to any of the preceding claims, wherein the polyether polyol (b2) has an average functionality of from 1.9 to 5.9, preferably from 2.0 to 4.8, more preferably from 2.0 to 4.0, more preferably from 2.5 to 3.5, and especially preferably from 2.9 to 3.1.

7. The composite element according to any of the preceding claims, wherein the polyether polyol (b2) has a number average molecular weight of 0.15x10³g/mol to 4.0x 10³g/mol, preferably between 0.15X10³g/mol to 2.0x 10³g/mol, more preferably between 0.15X10³g/mol to 1.0x 10³g/mol, and particularly preferably between 0.15X10³g/mol to 0.6x 10³g/mol.

8. The composite element according to any one of the preceding claims 2 to 7, wherein the weight of polyether polyols (b1) and (b2) is based on the total weight of the mixture consisting of polyether polyols (b1) and (b 2).

9. The composite element of any preceding claim wherein the difference in number average molecular weight of polyether polyols (b1) and (b2) is at least 0.5x 10³g/mol, preferably at least 1.0X 10³g/mol, more preferably at least 2.0x 10³g/mol, and particularly preferably at least 3.5X 10³g/mol。

10. The composite member of any of the preceding claims, wherein a chain extender is present.

11. The composite element according to the preceding claim, wherein the chain extender comprises a mixture of diols having from 2 to 8 carbon atoms, preferably having from 4 to 6 carbon atoms, and the chain extender particularly preferably comprises dipropylene glycol and butanediol.

12. The composite element according to any one of the preceding claims, wherein the compound having isocyanate groups comprises the isocyanates diphenylmethane 2,4' -, 2' -and/or 4,4' -diisocyanate (MDI) and/or polyphenyl polymethylene polyisocyanate, more preferably polyphenyl polymethylene polyisocyanate.

13. The composite element according to any one of the preceding claims, wherein the hardness of the polyurethane is greater than 45 shore D, preferably greater than 55 shore D, measured according to DIN 53505.

14. A method for preparing a composite element according to any one of the preceding claims, comprising mixing

(a) A compound containing at least two isocyanate groups, with

(b) A polyether polyol, wherein the polyether polyol (b) is a mixture of ingredients comprising at least polyether polyol (b1) and polyether polyol (b2),

optionally in the presence of

(c) Catalyst and/or

(d) Auxiliary and/or additive and/or

(e) A chain extender, and curing the mixture in contact with the metal layer.

15. The process according to the preceding claim, wherein the compound a) comprising isocyanate groups has an NCO content of from 20% to 40%, preferably from 20% to 35%, more preferably from 20% to 32%.

16. The process according to any of the preceding claims, wherein the mixture optionally comprising (c) catalyst, (d) auxiliaries and/or additives and/or chain extenders (e) has a viscosity of less than 6.0x10 measured at 23 ℃ according to DIN 53019-1³mPas, preferably less than 5.0x 10³mPas, more preferably less than 4.0x 10³mPas。

17. The process according to the preceding claim, wherein the compound (a) comprising isocyanate groups is a diisocyanate and has a molecular weight of from 0.076 to 2x 10³Addition products of polyols in g/mol.

18. Composite element obtainable by the method according to any one of the preceding claims.

19. Use of a composite element according to any one of the preceding claims in a vehicle, a watercraft, an aircraft or a building structure.

20. A vehicle, watercraft, aircraft or building structure comprising a composite element according to any preceding claim.

Example (b):

feeding:

polyol 1: polyether alcohols prepared by alkoxylation of propylene glycol with propylene oxide and ethylene oxide, having a functionality of 1.76, a molecular weight of 3350g/mol and an OH number of 29.5mg KOH/g

Polyol 2: polyether alcohols prepared by alkoxylation of sucrose, glycerol with propylene oxide and ethylene oxide, having a functionality of 4.15, a molecular weight of 5250g/mol and an OH number of 44mg KOH/g

Polyol 3: polyether alcohols prepared by alkoxylation of ethylenediamine with propylene oxide having a functionality of 4, a molecular weight of 300g/mol and an OH number of 750mg KOH/g

Polyol 4: polyether alcohols prepared by alkoxylation of glycerol with propylene oxide and ethylene oxide having a functionality of 2.49, a molecular weight of 5170g/mol and an OH number of 27mg KOH/g

Polyol 5: polyether alcohols prepared by alkoxylation with propylene oxide p-toluenediamine having a functionality of 3.9, a molecular weight of 550g/mol and an OH number of 398mg KOH/g

Polyol 6: polyether alcohols prepared by alkoxylation of trimethylolpropane with propylene oxide, having a functionality of 3.0, a molecular weight of 200g/mol and an OH number of 860mg KOH/g

KV 1: dipropylene glycol

KV 2: butane-1, 4-diol

Zeo: zeolite paste, 50% in castor oil

DF: AF 9000 antifoaming/antifoaming agent

ISO 1: lupranat MP 102 (prepolymer based on 4,4' MDI prepolymer and polyether polyol having an NCO content of 23% and a viscosity at 25 ℃ of 650mPas) from BASF Polyurethanes GmbH

ISO 2: lupranat M20S (polymeric MDI having an NCO content of 31.5% and a viscosity at 25 ℃ of 210mPas) from BASF Polyurethanes GmbH

ISO 3: lupranat MP 105 (prepolymer based on 4,4' -MDI, PMDI and polyether polyol having an NCO content of 28.5% and a viscosity at 25 ℃ of 120mPas) from BASF Polyurethanes GmbH

ISO 4: ISO 136/26 (prepolymer based on 4,4' MDI and polyether polyol having an NCO content of 18% and a viscosity of 1200mPas at 25 ℃) from BASF Polyurethanes GmbH

ISO 5: ISO 137/28 (prepolymer based on 4,4' MDI and polyether polyol having an NCO content of 18% and a viscosity of 750mPas at 25 ℃) from BASF Polyurethanes GmbH

ISO 6: ISO 136/94 (prepolymer based on 4,4' MDI and polyether alcohol) from BASF Polyurethanes GmbH, having an NCO content of 5.8% and a viscosity of 5500mPas at 50 ℃

ISO 7: blend of 48.5% ISO4 with 51.5% ISO5

To prepare the polyol mixture, the ingredients of the polyol component (polyols, additives, etc.) are first mixed. Subsequently, the polyol component was reacted with the indicated isocyanate in the mixing ratio indicated in the table. The mixing ratio is selected such that the equivalent ratio of NCO groups in the isocyanate to the sum of reactive hydrogen atoms in the compound reactive with isocyanate is 1.09: 1. For the determination of the hardness or storage modulus, test specimens having a thickness of 1cm or test sheets having a thickness of 2mm were prepared.

The preparation is realized as follows:

the temperature of the polyol mixture and the isocyanate component was room temperature (25 ℃). The only exception is the isocyanate component ISO 136/94. It is treated at a temperature of 50 ℃. To prepare the test specimens, the appropriate amount of polyol component is initially charged and the appropriate amount of isocyanate component is added. Then by Speedmixer from Hauschild^TMThe reactive mixture was mixed at 800rpm for 5 seconds and then 1800rpm for 55 seconds. The homogeneously mixed reaction mixture is then introduced into a mold which is preheated to 100 ℃ correspondingly. After 1 hour at 100 ℃, the test specimens were demolded.

The hardness of the material was measured on a sheet 1cm thick. For this purpose, the sheets were first conditioned at room temperature for 7 days. Hardness was measured analogously to DIN 53505. To determine the hardness at 50 ℃ and 100 ℃, the materials were stored in corresponding ovens at the appropriate temperature for 3 hours. The hardness was then measured directly in an oven at the appropriate temperature to avoid cooling of the material.

The examples following table 1 are intended to illustrate the effect of the compositions of the present invention.

TABLE 1

n.d. -, was not determined due to the too low shore hardness of the material at Room Temperature (RT)

As is apparent from comparative examples V1 to V4,

it is apparent from example B1 that a polyurethane having the desired properties in the range from-45 ℃ to +50 ℃ and an elastic modulus >275MPa is obtained. The polyurethanes obtained in V1 to V4 have a low hardness at 50 ℃ and therefore a low modulus of elasticity well below 275 MPa. The specific combination of isocyanates (a) with NCO contents > 20% by weight with suitable polyol mixtures (b) gives suitable polyurethanes. This is illustrated in examples B2 to B4 relative to comparative examples V5 and V6.