阅读说明：本技术 聚酯多元醇的半结晶混合物及其用途 (Semi-crystalline mixtures of polyester polyols and use thereof ) 是由 A·布兰特 H·贝克 A·库克斯 K·施罗德 于 2018-06-04 设计创作，主要内容包括：本发明涉及聚酯多元醇的半结晶混合物,其在熔融时重结晶并且可以通过使反应混合物缩聚来获得,所述反应混合物包含一种或多种二羧酸,选自具有至少8的偶数个亚甲基的饱和脂族二羧酸,和一种或多种二醇,选自具有至少一个醚官能团的脂族二醇。本发明还涉及聚合物材料,其由用含有至少一个异氰酸酯基和/或环氧基团的有机化合物对聚酯多元醇的混合物的化学改性得到。根据本发明的混合物和材料的特征在于相对低的熔融焓,同时熔融温度可以设定在-30至60℃的范围内,这表示可以获得含有根据本发明的混合物和材料的易于熔化的配制物。根据本发明的混合物和材料还提供具有高弹性和抗断裂性的这种配制物。因此,本发明包括根据本发明的聚酯多元醇和聚合物材料在热塑性材料中作为变形、熔融和挤出手段的用途,以及其用于制备粘合剂和密封剂、特别是热熔性粘合剂和反应性粘合剂的用途。(The invention relates to a semi-crystalline mixture of polyester polyols, which recrystallizes when molten and can be obtained by polycondensing a reaction mixture comprising one or more dicarboxylic acids selected from saturated aliphatic dicarboxylic acids having an even number of methylene groups of at least 8, and one or more diols selected from aliphatic diols having at least one ether function. The invention also relates to polymeric materials obtained by chemical modification of a mixture of polyester polyols with an organic compound containing at least one isocyanate and/or epoxy group. The mixtures and materials according to the invention are characterized by a relatively low enthalpy of fusion, while the melting temperature can be set in the range of-30 to 60 ℃, which means that readily meltable formulations containing the mixtures and materials according to the invention can be obtained. The mixtures and materials according to the invention also provide such formulations with high elasticity and fracture resistance. The invention therefore includes the use of the polyester polyols and polymer materials according to the invention as a means of deformation, melting and extrusion in thermoplastic materials, and their use for producing adhesives and sealants, in particular hot melt adhesives and reactive adhesives.)

1. Semi-crystalline mixtures of polyester polyols, which recrystallize when molten, obtainable by polycondensation of reaction mixtures comprising one or more dicarboxylic acids and one or more diols, wherein

(a) At least 50 mol% of the dicarboxylic acids are selected from saturated aliphatic dicarboxylic acids having neither tertiary nor quaternary carbon atoms with an even number of methylene groups of at least 8; and

(b) at least 40 mole% of the glycol is selected from aliphatic glycols having at least one ether functional group but no tertiary or quaternary carbon atoms.

2. Mixture according to claim 1, characterized in that at least 60 mol%, preferably at least 70 mol%, of the dicarboxylic acids are selected from the dicarboxylic acids according to component a) of the reaction mixture.

3. Mixture according to one or both of claims 1 and 2, characterized in that at least 60 mol%, preferably at least 70 mol%, of the diols are selected from the diols according to component b) of the reaction mixture.

4. Mixture according to one or more of the preceding claims, characterized in that the dicarboxylic acid according to component a) has not more than 24 methylene groups, preferably not more than 18 methylene groups, particularly preferably not more than 16 methylene groups, but preferably at least 10 methylene groups.

5. Mixture according to one or more of the preceding claims, characterized in that the aliphatic diol of component b) is selected from the general formula H- ([ O- (CH)₂)_m]_x-[O-(CH₂)_n]_y)_z-OH, wherein m, n are positive integers from 1 to 4, x, y are non-negative integers, wherein x + y is at least 1, and z is a positive integer, wherein (x + y) z is at least 2 and z (x (m +1) + y (n +1)) is less than 40, wherein preferably m is 2, x is 1, y is 0, and z is preferably less than 10, more preferably less than 8, more preferably less than 6.

6. Mixture according to one or more of the preceding claims, characterized in that the proportion of dicarboxylic acids which do not have a saturated aliphatic dicarboxylic acid with an even number of methylene groups of at least 8 but at least 9 carbon atoms is less than 20 mol%, preferably less than 10 mol%, particularly preferably less than 4 mol%, relative to the total proportion of dicarboxylic acids in the reaction mixture.

7. Mixture according to one or more of the preceding claims, characterized in that, in addition to the dicarboxylic acids representing saturated aliphatic dicarboxylic acids having an even number of methylene groups of at least 8, aromatic dicarboxylic acids and/or unsaturated dicarboxylic acids having less than 9 carbon atoms, which are preferably selected from isophthalic acid, terephthalic acid, phthalic acid, furandicarboxylic acid, itaconic acid, fumaric acid and/or maleic acid, are contained, wherein their proportion, relative to the total proportion of dicarboxylic acids, is preferably at least 2 mol%, preferably at least 8 mol%, particularly preferably at least 15 mol%, but preferably less than 40 mol%, particularly preferably less than 30 mol% in total.

8. Mixture according to one or more of the preceding claims, characterized in that the proportion of diols which do not represent diols according to component b) and which simultaneously have at least one ether function and a tertiary and/or quaternary carbon atom is less than 20 mol%, preferably less than 10 mol%, particularly preferably less than 4 mol%, based on the total proportion of diols.

9. Mixture according to one or more of the preceding claims, characterized in that, in addition to the diol according to component b), an aliphatic diol having no ether function and no more than 10 carbon atoms, preferably selected from ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol and/or 1, 8-octanediol, is contained, wherein their proportion is preferably at least 1 mol%, but preferably less than 40 mol%, particularly preferably less than 20 mol% and very particularly preferably less than 10 mol%, relative to the total proportion of diols.

10. Mixture according to one or more of the preceding claims, characterized in that the reaction mixture additionally contains unbranched β -, γ -, δ -and/or ε -hydroxycarboxylic acids, which may also be present in their lactone form, in a proportion of preferably at least 1 mol%, but preferably less than 35 mol%, particularly preferably less than 22 mol%, based on the total proportion of dicarboxylic acids.

11. Mixture according to one or more of the preceding claims, characterized in that the proportion of other condensable organic compounds which do not represent dicarboxylic acids or diols or hydroxycarboxylic acids according to claim 10 in the reaction mixture is less than 10% by weight, relative to the total proportion of dicarboxylic acids and diols.

12. Mixture according to one or more of the preceding claims, characterized in that the diol is contained in the reaction mixture in molar excess with respect to the dicarboxylic acid, but preferably in an excess of not more than 1.2: 1.

13. Mixture according to one or more of the preceding claims, characterised in that the acid value of the mixture is less than 50mg KOH/g, preferably less than 10mg KOH/g, particularly preferably less than 5mg KOH/g, particularly preferably less than 2mg KOH/g, the hydroxyl value being in the range from 10 to 150mg KOH/g, preferably in the range from 20 to 120mg KOH/g.

14. A polymeric material obtainable by adding such an organic compound containing at least one epoxy and/or isocyanate group, preferably at least two of these groups, more preferably at least two isocyanate groups, to the terminal hydroxyl groups of a mixture according to one or both of claims 12 and 13.

15. Use of a mixture according to one or more of claims 1 to 13 or a material according to claim 14 as a thermoplastic material or as a component of an adhesive and/or sealant.

The implementation mode is as follows:

in the following, the preparation of the polyester polyol mixtures according to the invention is described and the corresponding melting behaviour is characterized by dynamic differential calorimetry (DSC) and compared with polyester polyols prepared from dicarboxylic acids and diols which are not components a) or b) according to the first claim of the present invention.

The preparation of the polyester polyol mixture was carried out according to the following scheme:

in a1 liter four-necked flask equipped with a nitrogen bleed, a thermostat, a paddle stirrer and distillation arms, a quantity of dicarboxylic acid and a corresponding quantity of diol in molar excess relative to the quantity of dicarboxylic acid were provided and mixed. The reaction mixture was heated and stirred at a temperature of 200 ℃ for about 8 hours in a nitrogen stream. Then, the reaction mixture was cooled, and 0.02% by weight of tetraisopropyl titanate with respect to the reaction mixture was added. Subsequently, the reaction mixture was heated to 200 ℃ and the pressure in the reaction flask was gradually reduced to 30 mbar. The acid number is continuously controlled as set forth in detail in the description of the invention. Once the acid value of the reaction mixture had dropped to a value below 3mg KOH/g, the reaction mixture was first cooled to 80 ℃ and cooled, and then the reaction mixture was further cooled to room temperature. The acid and hydroxyl values were then finally determined at 20 ℃ and the mixture was chromatographically characterized.

For chromatographic characterization by Gel Permeation Chromatography (GPC), a sample of the reaction mixture was dissolved with tetrahydrofuran and applied to the column, followed by elution with tetrahydrofuran. Gel Permeation Chromatography (GPC) with RI detector was performed at column oven temperature of 40 ℃ and temperature in detector of 40 ℃ after calibration by polystyrene standard. The relative number average molecular weight and the weight average molecular weight value were determined from the molecular weight distribution curve, and the polydispersity was determined therefrom.

Table 1 shows each weighed sample and the specific monomers used to prepare each polyester polyol.

The polyester polyols prepared according to table 1 were measured by differential calorimetry, in which a sample of the reaction mixture was first heated to 150 ℃ and then brought to-90 ℃ at a cooling rate of 10 kelvin/min. After 10 minutes at-90 ℃, a sample of the reaction mixture was heated to 150 ℃ at a rate of 10 kelvin/minute and a DSC chart was recorded.

Fig. 1 shows a characteristic DSC diagram of a mixture of polyester polyols according to the invention based on specific example a-1, which shows the effect of an exothermic recrystallization superimposed on an endothermic melting process.

As can be seen from FIG. 2, the polyester polyol mixtures (A-2) and (A-3) according to the invention have exothermic recrystallization peaks superimposed on the melting process. When using polyethylene glycol, the melting process can be shifted to a significantly lower temperature range of 0-20 ℃, wherein the ratio of the recrystallized phase to the endothermic melting peak remains almost unchanged, thus continuing to obtain a fusible polyester polyol mixture.

The mixture of 2, 5-furandicarboxylic acid (A-3) or isophthalic acid (B-1) hardly reduces the recrystallization behavior, so that the shift of the melting range does not occur.

In contrast, as is clear from example V-1 in FIG. 4, the crystallinity is not the cause of the existence of recrystallization, and the structural characteristics caused by the chemical composition lead to the effect of recrystallization, so it is not effective to use only a linear diol having no ether functional group. Polyester polyols obtained from dicarboxylic acids having a number of methylene groups which lags the number required in the present invention give similar results, providing only amorphous materials which do not have the desired mechanical stability and elasticity.

The variation of the chain length of the dicarboxylic acids in the polyester polyol mixture according to the invention, with each additional ethylene unit, shifts the melting range towards higher temperatures by about 10 ℃ and is therefore suitable for the particular application (see examples B-1, B-2 and B-3 in FIG. 3).