阅读说明：本技术 多元醇组分及其用于制备硬质聚氨酯泡沫的用途 (Polyol component and use thereof for producing rigid polyurethane foams ) 是由 H·瓦格纳 钟满福 S·扎巴克史 于 2020-03-19 设计创作，主要内容包括：本发明涉及一种包含至少三种不同的聚醚多元醇A)至C)的多元醇组分P)、使用多元醇组分P)制备硬质聚氨酯泡沫的方法、以及由其制备的硬质聚氨酯泡沫。(The invention relates to a polyol component P) comprising at least three different polyether polyols A) to C), to a method for producing rigid polyurethane foams using the polyol component P), and to rigid polyurethane foams produced therefrom.)

1. A polyol component P) comprising:

a) one or more polyether polyols A) having an OH number of from 300 to 520mg KOH/g, selected from the reaction products of: monosaccharides, oligosaccharides, polysaccharides, polyols, alkoxylation products of the above compounds, or mixtures thereof;

b) one or more polyether polyols B) having an OH number of from 320 to 500mg KOH/g, selected from the reaction products of aromatic diamines and alkylene oxides;

c) one or more polyether polyols C) having an OH number of from 15 to 60mg KOH/g, selected from the group consisting of the reaction products of monosaccharides, oligosaccharides, polysaccharides, polyols, water or mixtures thereof with alkylene oxides;

d) optionally one or more polyols D) which are different from the polyether polyols A), B) and C);

e) optionally one or more catalysts E);

f) optionally one or more further components F) selected from auxiliaries and adjuvants,

g) optionally one or more blowing agents selected from chemical blowing agents G1) and physical blowing agents G2).

2. Polyol component P) according to claim 1, wherein the functionality of the polyether polyol a) is from 4.6 to 6.5.

3. Polyol component P) according to claim 1 or 2, wherein the functionality of the polyether polyol B) is from 3.0 to 4.0.

4. Polyol component P) according to any of claims 1 to 3, wherein the polyether polyol B) is selected from 2, 3-toluenediamine, 3, 4-toluenediamine, 2, 5-toluenediamine, 2, 6-toluenediamine or mixtures thereof and C₂-C₄A reaction product of an alkylene oxide.

5. The polyol component P) according to any of claims 1 to 4, wherein the functionality of the polyether polyol C) is from 2.3 to 5.5.

6. The polyol component P) according to any of claims 1 to 5, wherein the functionality of the polyether polyol C) is from 2.5 to 4.5.

7. Polyol component P) according to one of claims 1 to 6, wherein the functionality of polyether polyol C) is from 2.3 to 5.5 and the OH number of polyether polyol B) is from 380 to 450mg KOH/g.

8. Polyol component P) according to any of claims 1 to 7, wherein the polyether polyol C) has a functionality of from 2.3 to 5.5 and is selected from the group consisting of reaction products of monosaccharides, oligosaccharides, polysaccharides, polyols, water or mixtures thereof with ethylene oxide and propylene oxide.

9. Polyol component P) according to any of claims 1 to 8, wherein the polyether polyol C) is selected from the reaction products of monosaccharides, oligosaccharides, polysaccharides, polyols or mixtures thereof with ethylene oxide and propylene oxide.

10. According to any one of claims 1 to 9The polyol component P) described above, wherein the polyether polyol C) is selected from glycerol, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, pentaerythritol, sorbitol, sucrose, water or mixtures thereof with C₂-C₄A reaction product of an alkylene oxide.

11. Polyol component P) according to any of claims 1 to 10, wherein polyether polyol C) comprises from 5 to 35% by weight of ethylene oxide units, based on the total weight of polyether polyol C).

12. Polyol component P) according to any of claims 1 to 11, wherein polyether polyol C) has the following structure:

wherein S is selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides, water, and polyols;

n is 2 to 10;

b is in each case, independently of one another at each occurrence, a chain of ethylene oxide and propylene oxide units, wherein the ethylene oxide and propylene oxide units form a pure ethylene oxide block, a pure propylene oxide block and/or a mixed block of ethylene oxide and propylene oxide, and the end blocks comprise from 10 to 100% by weight of ethylene oxide units, based on the total weight of the end blocks.

13. The polyol component P) according to any of claims 1 to 12, wherein the concentration of polyether polyol C) is at least 2% by weight, based on the total amount of components a) to G1) of the polyol component P).

14. The polyol component P) according to any one of claims 1 to 13, comprising:

a)35 to 70 wt% of one or more polyether polyols a;

b)5 to 50 wt% of one or more polyether polyols B;

c)2 to 30 wt% of one or more polyether polyols C;

d)0 to 40% by weight of one or more polyols D);

e) optionally one or more catalysts E);

f) optionally one or more further components F) selected from auxiliaries and adjuvants;

g) optionally one or more blowing agents selected from chemical blowing agents G1) and physical blowing agents G2);

wherein the concentration values of A) to D) in% by weight are based on the total amount of components A) to G1) of the polyol component P).

15. The polyol component P) according to any of claims 1 to 14, wherein the polyol component P) comprises at least one further polyol D) selected from polyether polyols D1), the polyether polyols D1) having an OH value of 100 to 240mg KOH/g, selected from the reaction products of amines, polyols or mixtures thereof with alkylene oxides.

16. Polyol component P) according to any one of claims 1 to 15, wherein the polyol component P) comprises at least one further polyol D1) selected from polyether polyols having an OH value of from 100 to 240mg KOH/G, selected from the reaction products of amines, polyols or mixtures thereof with alkylene oxides, wherein the total concentration of polyether polyols C) and D1) is at least 5% by weight, based on the total amount of components a) to G1) of the polyol component P).

17. A process for preparing a rigid polyurethane foam by reacting:

I) diisocyanate or polyisocyanate PI) or mixtures thereof, with

II) a polyol component P) according to any of claims 1 to 16.

18. A rigid polyurethane foam obtainable by the process of claim 17.

19. Use of a polyol component P) according to any of claims 1 to 16 for the preparation of rigid polyurethane foams.

20. Use of rigid polyurethane foam prepared by the process according to claim 17 for thermal insulation and refrigeration applications.

Examples

I. The measuring method comprises the following steps:

measurement of hydroxyl value:

the hydroxyl number is determined in accordance with DIN 53240 (1971-12).

And (3) viscosity measurement:

unless otherwise stated, the polyol viscosity was determined at 25 ℃ in accordance with DIN EN ISO 3219(1994), using Haaker viscotest 550 or Brookfield CAP2000 with plate/cone measurement geometry (PK100), using PK 11 (diameter: 28 mm; cone angle: 1 ℃ C.) and a shear rate of 401/s.

Measurement of mold release characteristics:

the release characteristics were determined by measuring the post-foaming of foams prepared using box molds of dimensions 700x400x90mm at mold temperatures of 45 ± 2 ℃, depending on the release time and degree of overfilling (OP, which corresponds to the ratio of total apparent density/minimum filled density and describes the additional percentage content of raw material actually required to just fill the mold with rigid PU foam the experimental examples described herein were performed at 17.5% OP). Post-foaming was determined by measuring the height of the foam cuboid after 24 h.

Start time:

the time from the start of mixing of the reaction mixture to the start of expansion of the foam.

Set time (gel time/fiber time)

The reaction mixture is mixed from the start until the time at which the fibers in contact with the foam can be pulled out (e.g., using a wooden stick). This therefore represents a transition from the liquid state to the solid state.

Minimum filling density/free foaming density of component parts:

the minimum packing density is determined by the following method: one part of the polyurethane reaction mixture was introduced into a mold of size 2000x200x50mm at a mold temperature of 45 ± 2 ℃ to fill the mold with foam exactly without touching the ends of the mold. The length of the flow path is measured and the minimum fill density is calculated from MFD (m L/(V s)), where m is the mass, L is the length of the mold, s is the flow path and V is the volume of the mold. The free foam density was determined by foaming the polyurethane reaction mixture into plastic bags at room temperature. The density was determined on cubes sampled from the center of a foam-filled plastic bag.

Determination of flowability:

flowability is reported as the flow factor (minimum packing density/free rise density).

Adhesion:

the test body was sampled from the sample. The test body corresponds to the first 50cm of the lance-shaped molded article as viewed from the gate, and the degree of overfilling is 14.5%. Using a stencil, the aluminum foil was cut into 56mm wide and 200mm long pieces on the top surface and pulled up from the foam to give an approximately 50mm piece. The sheet was clamped in the sample holder of a universal testing machine. After the test time is reached, the measurement is started. The measured force for peeling the aluminum foil from the foam is output in newtons (N). The adhesion values intended for comparison with other foam formulations must be measured under the same foaming and testing conditions. To test the adhesion limit of the cover foil to the foam, the mold temperature was lowered in 5 ℃ steps, the sample was foamed, and the adhesion was measured on the sample. The adhesion limit was reached when the cover layer had detached from the foam when the sample was demolded.

Thermal conductivity:

thermal conductivity was measured using a Taurus TCA300 DTX instrument at a midpoint temperature of 10 ℃. To prepare the test samples, the polyurethane reaction mixture was introduced into a mold of size 2000x200x50mm (overfill of 15%) and demolded after 5 minutes. After 24 hours of storage under standard conditions, several foam cuboids of size 200x200x50mm (at the 10mm, 900mm and 1700mm positions from the start of the lance) were cut from the center. Then, the top and bottom sides were removed to obtain test samples of size 200x200x30 mm.

Preparation of polyols

Polyether polyols a1) and a 2):

the pressure reactor with stirrer, jacket heating and cooling, metering devices for solid and liquid substances and alkylene oxide, as well as devices for nitrogen inertization and a vacuum system was charged with glycerol, sucrose, solid imidazole, and, for polyol a1, with a polyether polyol based on sucrose, glycerol and propylene oxide (OH value 490mg KOH/g, functionality: 4.3). The reactor was then inerted repeatedly (with stirring) and the temperature was increased to 120 ℃. The mixture was reacted with propylene oxide at 120 ℃. The post-reaction was carried out at 120 ℃ for 2 hours. The sample was subsequently stripped in a stream of nitrogen gas.

Examples of calculating the functionality from the polyether polyol A1)

12.3kg of glycerol, 90.70kg of sucrose, 0.34kg of solid imidazole and 29.00kg of a polyether polyol based on sucrose, glycerol and propylene oxide (molecular weight 488g/mol, functionality 4.3) were reacted with 256.3kg of propylene oxide to give 372kg of product having the following parameters:

OH number 429mg KOH/g

Viscosity (25 ℃ C.) 34600 mPas

Calculation of starter functionality:

glycerol (functionality 3): 12300 g/92.09g/mol 132.4mol

Sucrose (functionality 8): 90700 g/342.3g/mol 246.97mol

Imidazole (functionality 1): 340g/68.08 g/mol-5.0 mol

Polyether polyol (functionality 4.3): 29000 g/488g/mol 59.4mol

Initiator functionality: (132.4mol × 3+246.97mol × 8+5.0mol × 1+59.4mol × 4.3)/(132.4mol +246.97mol +5.0mol +59.40mol) ═ 6.0

The composition (mass percent) is as follows:

polyether polyol B1):

the pressure reactor with stirrer, jacket heating and cooling, metering devices for solid and liquid substances and alkylene oxide, as well as devices for nitrogen inertization and a vacuum system was heated to 80 ℃ and inertization was repeated. The reactor was charged with o-toluenediamine and the stirrer was started. The reactor was then inertized again, the temperature was increased to 130 ℃ and propylene oxide was metered in. After a reaction time of 2 hours, the temperature was lowered to 100 ℃ and dimethylethanolamine was added. The intermediate is reacted with additional propylene oxide. The post-reaction was carried out at 130 ℃ for 2 hours. The sample was subsequently stripped in a stream of nitrogen gas.

Polyether polyols C1) and C2):

polyether polyol C1

A pressure reactor with stirrer, jacket heating and cooling, metering devices for solid and liquid substances and alkylene oxide, as well as devices for nitrogen inertization and a vacuum system was charged with 11.59kg of glycerol and 1kg of aqueous KOH solution (48% by mass). The reactor was then inertized repeatedly (with stirring), the temperature was raised to 120 ℃ and a reduced pressure (15 mbar) was applied for 1 hour. 106.70kg of propylene oxide were then metered in. In the next step, a mixture of 234.81kg of propylene oxide and 46.76kg of ethylene oxide was metered in. The post-reaction was carried out at 120 ℃ for 2 hours. The sample was subsequently stripped in a stream of nitrogen and post-treated with Magnesol. This resulted in a product with the following parameters:

OH value: 56mg KOH/g

Viscosity (25 ℃): 480mPas

Polyether alcohol C2

A pressure reactor with stirrer, jacket heating and cooling, metering devices for solid and liquid substances and alkylene oxide, and also devices for nitrogen inertization and a vacuum system was charged with 9.19kg of glycerol and 1kg of aqueous KOH solution (48% by mass). The reactor was then inertized repeatedly (with stirring), the temperature was raised to 120 ℃ and a reduced pressure (15 mbar) was applied for 1 hour. 337.31kg of propylene oxide were then metered in. In the next step, 53.15kg of ethylene oxide are metered in. The post-reaction was carried out at 120 ℃ for 2 hours. The sample was subsequently stripped in a stream of nitrogen and post-treated with Magnesol. This resulted in a product with the following parameters:

OH value: 35mg KOH/g

Viscosity (25 ℃): 850mPas

Polyether polyol D1)

The pressure reactor, equipped with a stirrer, jacket heating and cooling, metering devices for solid and liquid substances and alkylene oxide, as well as devices for nitrogen inertization and a vacuum system, was heated to 80 ℃ and inertization was repeated. O-toluenediamine is added and the reactor is inertized repeatedly. The temperature was increased to 130 ℃ and the mixture was mixed with a mixture of ethylene oxide and propylene oxide (EO: PO ═ 1:15) at this temperature. After a reaction time of 2 hours, 50% KOH in water (mass%) was added. This was followed by a decompression phase of 1 hour, after which a mixture of ethylene oxide and propylene oxide (EO: PO. RTM.1: 15) was metered in at 130 ℃. After a reaction time of 3 hours, the sample was stripped in a stream of nitrogen.

III. raw materials

The polyols A) to D) are prepared as described above.

Polyol a 1): a sucrose, glycerol and Propylene Oxide (PO) -based polyether polyol having an OH number of 427mg KOH/g; functionality: 6.0

Polyol a 2): a sucrose, glycerol and PO based polyether polyol having an OH number of 450mg KOH/g; functionality: 5.0

Polyol B1): polyether polyols based on ortho-TDA and PO having an OH value of 399 mgKOH/g; functionality: 4.0

Polyol C1): a glycerol, propylene oxide and Ethylene Oxide (EO) based polyether polyol, the alkylene oxide chain consisting of PO and a terminal mixed PO/EO block, wherein the proportion of EO in the polyether polyol is 11.7 wt.%, based on the polyether polyol, and the proportion of EO in the terminal PO/EO block is 16.6 wt.%, based on the terminal block; OH value: 56 mgKOH/g; functionality: 3.0

Polyol C2): a glycerol, propylene oxide and ethylene oxide based polyether polyol, wherein the alkylene oxide chain consists of PO and EO blocks, wherein the proportion of EO in the polyether polyol is 13.3 wt.%, based on the polyether polyol, and the proportion of EO in the tipped EO blocks is 100 wt.%, based on the end groups; OH value: 35mg KOH/g; functionality: 3.0

Polyol D1): polyether polyols based on ortho-TDA, propylene oxide and ethylene oxide having an OH number of 160mg KOH/g; functionality: 4.0

Catalyst mixture E) consisted of the following:

catalyst E1): dimethyl cyclohexylamine

Catalyst E2): pentamethyldiethylenetriamine or bis (2-dimethylaminoethyl) ether

Catalyst E3): tris (dimethylaminopropyl) hexahydro-1, 3, 5-triazine

Catalyst E4): dimethylbenzylamine

Stabilizer F):

silicone-containing foam stabilizers from EvonikB8474 and/orB8491

Physical blowing agent G2)

Cyclopentane 95(CP 95): cyclopentane having a purity of 95%

Furthermore, each polyol component was additionally mixed with 13.5% by weight of cyclopentane 95, based on the total weight of the polyol components a) to G1).

Isocyanate:

polymeric MDI having an NCO content of 31.5% by weight (M20)

Rigid PU foams

The polyol component P) was prepared using the above-mentioned starting materials, to which a physical blowing agent was added before foaming. PU 30/80IQ high pressure with yield rate of 250g/s(Elastogran GmbH) was used to mix the polyol component P), which had been mixed with a physical blowing agent, with the specified isocyanate in the amount required in each case in order to obtain the desired isocyanate index.

The reaction mixture was injected into a mold adjusted to a temperature of 40 ℃ and having dimensions of 2000mm x200 mm x50mm or 400mm x 700mm x90mm and allowed to foam in the mold. The degree of overfilling was 17.5%, i.e.17.5% more reaction mixture was used than was required for complete foaming out of the mould.

Table 1 shows the measurement results of the polyol component P used and of the rigid PU foams prepared therefrom. From the results it is evident that the rigid PU foams prepared using the polyol component P) of the invention have an improved combination of advantageous properties, namely mold release (lower values visible in the table for post-foaming), thermal insulation and, in particular, improved adhesion.

TABLE 1