阅读说明：本技术 含酰亚胺的聚酯 (Imide-containing polyesters ) 是由 M.舍德勒 H.内夫茨格 N.迈内 G.耶格 T.哈根 M.贝克尔 P.诺德曼 于 2018-11-27 设计创作，主要内容包括：本发明涉及制备羟基封端的含酰亚胺基团的聚酯醇的特定方法、这些聚酯本身,及其用于制备聚氨酯的用途。(The present invention relates to a specific process for preparing hydroxyl-terminated, imide group-containing polyesterols, to these polyesters themselves, and to their use for preparing polyurethanes.)

1. A process for preparing hydroxyl-terminated polyesterols (A) which comprises,

in a first process step, an imide group-containing monocarboxylic or polycarboxylic acid (B) is first prepared by reacting components (B.1) and (B.2) in the presence of (C)

(B.1) at least one amino acid having one or more amino groups and one or more acid groups

(B.2) at least one carboxylic anhydride having exactly one anhydride group and no further free acid groups

(C) At least one diol and/or polyol having a molecular weight of 62 to 1000g/mol,

and in a second process step, esterifying the reaction mixture obtained in the first process step under polycondensation conditions

-without purification,

optionally adding further components B.2 and/or further components C and/or (D) further monocarboxylic and/or polycarboxylic acids which do not fall under the definition of components (B) and (B.2),

wherein optionally adjuvants and additives (E) and (E) are used in the first process step and/or in the second process step

Wherein no further solvent is added in the first process step, apart from component (C).

2. The process as claimed in claim 1 or 2 for preparing hydroxyl-terminated polyesterols (A), characterized in that the first process step is carried out at a temperature of from 25 ℃ to 200 ℃, preferably from 80 to 180 ℃, and the second process step is carried out at a temperature of from 150 to 250 ℃, preferably from 180 to 220 ℃, and under reduced pressure of from 0.1 to 300 mbar, preferably from 1 to 200 mbar.

3. Hydroxyl-terminated polyesterols (A) obtainable by the process as claimed in claim 1 or 2 and preferably having a melting point of <23 ℃, particularly preferably ≦ 20 ℃.

4. The process as claimed in claim 1 or 2 or the hydroxyl-terminated polyesterol (A) as claimed in claim 3, wherein in the preparation of the hydroxyl-terminated polyesterol (A) in addition to components (B.1), (B.2), (C), (D) and (E) further components (F) are used which are diols and polyols which do not fall under the definition of component (C) and wherein the proportion of components (B.1), (B.2), (C), (D) and (E) is > 80, preferably > 90, particularly preferably > 95,% by weight of the total amount of all components used.

5. A process as claimed in claim 1 or 2 or a hydroxyl-terminated polyesterol (A) as claimed in claim 3, wherein in the preparation of the hydroxyl-terminated polyesterol (A) only components (B.1), (B.2), (C), (D) and (E) are used.

6. A process as claimed in claim 1 or 2,4 or 5 or a hydroxyl-terminated polyesterol (A) as claimed in any of claims 3 to 5, wherein in the reaction of components (B.1) and (B.2) the molar ratio of amino groups from the amino acid (B.1) to anhydride groups from the carboxylic anhydride (B.2) is from 1.5:1 to 1:1.5, preferably from 0.9:1 to 1:0.9, particularly preferably from 0.95:1 to 1: 0.95.

7. The process as claimed in claim 1 or 2 or 4 to 6 or the hydroxyl-terminated polyesterol (A) as claimed in any of claims 3 to 6, characterized in that the amino acid (B.1) is selected from the group consisting of monoamino monocarboxylic acids, monoamino dicarboxylic acids, diamino monocarboxylic acids and diamino dicarboxylic acids.

8. The process as claimed in claim 1 or 2 or 4 to 7 or the hydroxyl-terminated polyesterol (A) as claimed in any of claims 3 to 7, characterized in that the amino acid (B.1) is selected from the group consisting of anthranilic acid (anthranilic acid), m-aminobenzoic acid, p-aminobenzoic acid, alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, serine, threonine, tryptophan, tyrosine, valine, ornithine, 3-aminopropionic acid, 2-aminobutyric acid, 4-aminobutyric acid, 6-aminocaproic acid, 2-amino-2-methylpropionic acid, 11-aminoundecanoic acid, homoserine.

9. The process as claimed in claim 1 or 2 or 4 to 8 or the hydroxyl-terminated polyesterol (A) as claimed in any of claims 3 to 8, characterized in that the carboxylic anhydride (B.2) is selected from phthalic anhydride, tetrachlorophthalic anhydride, 3-chlorophthalic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, succinic anhydride, 1, 8-naphthalic anhydride, derivatives of the anhydrides mentioned, for example alkyl-or alkenylsuccinic acids having an unbranched or branched C1 to C24 alkyl or alkenyl chain, such as (1-dodecen-1-yl) or (2-dodecen-1-yl) succinic anhydride, n-octenylsuccinic anhydride, tetradecenylsuccinic anhydride, hexadecenylsuccinic anhydride, octadecenylsuccinic anhydride, alkyl-and/or alkenylmaleic acids having an unbranched or branched C1 to C24 alkyl or alkenyl chain, such as dimethyl maleic anhydride, n-dodecenyl maleic anhydride, and diels-alder adducts of furan with, for example, maleic anhydride.

10. The process as claimed in claim 1 or 2 or 4 to 9 or the hydroxyl-terminated polyesterol (A) as claimed in any of claims 3 to 9, characterized in that the diols and polyols (C) are selected from the group consisting of ethylene glycol, propane-1, 2-diol, propane-1, 3-diol, butane-1, 4-diol, 2-methylpropane-1, 3-diol, pentane-1, 5-diol, neopentyl glycol, hexane-1, 6-diol, 3-methylpentane-1, 5-diol, butane-2, 3-diol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and glycerol, oligomers of 1,1, 1-trimethylolpropane, pentaerythritol, castor oil, 1, 4-butanediol, Polyether polyols such as poly (oxyalkylene) polyols and polyester polyols.

11. The process as claimed in claim 1 or 2 or 4 to 10 or the hydroxyl-terminated polyesterol (A) as claimed in any of claims 3 to 10, characterized in that the monocarboxylic and/or polycarboxylic acid (D) is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, hexadecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, oleic acid, ricinoleic acid and furandicarboxylic acid.

12. The process as claimed in claim 1 or 2 or 4 to 11 or the hydroxyl-terminated polyesterol (A) as claimed in any of claims 3 to 11, characterized in that the hydroxyl-terminated polyesterol (A) has an OH number of 20 to 500 mg KOH/g and a number average functionality of 1.4 to 3.5.

13. The process as claimed in claim 1 or 2 or 4 to 12 or the hydroxyl-terminated polyesterol (A) as claimed in any of claims 3 to 12, characterized in that at least one of the components (B.1), (B.2), (C), (D), (E) and (F) is biobased.

14. Use of a hydroxyl-terminated polyesterol (A) as claimed in any of claims 3 to 13 for the preparation of polyurethanes, preferably polyurethane foams.

Examples

1. Method and material

1.1 raw materials used:

trimellitic anhydride (Fluka)

Anthranilic acid (Sigma-Aldrich)

Acetic acid (Fisher Scientific)

Glutaric acid, technical grade (L anxess AG)

Adipic acid (BASF)

Phthalic anhydride (My-ChemGmbH)

Diethylene glycol (Sigma-Aldrich)

Ethylene glycol (Ineos)

D L-glutamic acid (Sigma-Aldrich)

D L-aspartic acid (abcr)

D L-lysine (Sigma-Aldrich)

SnCl₂·2H₂O (Sigma-Aldrich)

Glycerol (Sigma-Aldrich)

3-amino-1-propanol (Acros-Organics)

Diethylene glycol terephthalate (Sigma-Aldrich)

L 2830： Desmophen^®L2830 (Covestro AG), an aliphatic polyether polyol having an OH number of 28 mg KOH/g, a molar mass of 4000 Da and approximately 90 mol% primary OH end groups and a viscosity of 860 mPas at 25 ℃

TCPP Levagard PP^®(L anxess AG), trichloroisopropyl phosphate

B 8433 Tegostab^®B844 (Evonik Industries AG), Silicone stabilizers

B 8325 Tegostab^®B8325 (Evonik Industries AG), Silicone silicon stabilizer

DB Desmorapid^®DB (Covestro AG), activators for the production of rigid polyurethane foams

1792 Desmorapid^®1792 (Covestro AG), diethylene glycol and potassium acetate containing preparations; trimerization catalyst

A30 Niax catalyst A-30 (Momentive Performance Materials Inc.), Tertiary amine, catalyst for Water reaction

117 Addocat^®117 (L anxess AG), tertiary amines, catalysts for urethane reactions

Water deionized water

N-pentane (Azelis)

44V70L Desmodur^®44V 70L (Covestro AG), MDI isocyanates having an NCO content of 30 to 32% by weight

T80 Desmodur^®T80 (Covestro AG), TDI isocyanate having an NCO content of at least 48% by weight

T65N Desmodur^®T65N (Covestro AG), TDI isocyanate with an NCO content of at least 48% by weight.

1.2 methods used

The analysis was performed as follows:

viscosity:

MCR 51 rheometer from Anton Paar, DIN 53019 using CP 50-1 measuring cone (diameter 50mm, angle 1) at 25, 100, 200 and 500 s^-1At a shear rate of (a). The polyester polyols of the invention and not of the invention exhibit viscosity values which are independent of shear rate.

Hydroxyl value: determined according to DIN 53240-1 (catalyst-free method, 6 months 2013).

Acid value: determined according to DIN 51639-1 (11 months 2014).

Amine value: determined according to DIN EN ISO 2114 (6.2002).

Apparent density: determined according to DIN EN ISO 845 (10 months 2009).

Combustion properties: for rigid foams, the determination is carried out in accordance with DIN 4102-1 (5 months 1998). Measured according to DIN 75200 (9 months 1980) for flexible foams.

Compression strength of rigid foam: the compressive stress was determined at 10% compression according to DIN EN ISO 844 (11 months 2014).

Compression strength of flexible foam: the compressive stress was determined at 40% compression according to DIN EN ISO 3386-1 (10 months 2015).

Opening content: determined according to DIN EN ISO 4590 (2016 month 12, method 1) with AccuPyc 1330.

Dimensional stability: measured according to DIN ISO 2796 (1 month 1986)

Melting point: it is determined whether the melting point of the polyesterol is below room temperature. For this purpose, the polyesterols were stored at room temperature (23 ℃) for at least 4 weeks after preparation and visually checked whether the polyols remained homogeneous and liquid. The polyesterols which crystallize, form solids or become turbid during storage are discarded.

2. Polyester synthesis

2.1 one-pot Synthesis of trimellitic anhydride/ethylene glycol/Glycerol/Aminopropanol/diethylene glycol terephthalate (non-indigenous) Inventive, comparative example according to FR 1445078A)

A2 liter four-necked round bottom flask equipped with a mechanical stirrer, heating mantle, bottom thermometer, nitrogen connection, diaphragm pump vacuum connection, and a 40cm packed column with attached column head and an intensive condenser was pre-charged with 300 g of ethylene glycol (4.83 mol), 46 g of glycerol (0.50 ml), 75 g of 3-amino-1-propanol (1.00 mol) while passing nitrogen. The mixture was heated to 50 ℃ and 192 g of trimellitic anhydride (1.00 mol) were added. The mixture was heated to 140 ℃ for 80 minutes to convert the amine and anhydride to the imide. The reaction mixture was cooled to 120 ℃ and 127 g of diethylene glycol terephthalate (1.00 mol) and catalyst (14 mg of SnCl) were added₂·2H₂O). The reaction mixture was heated to a bottom temperature of 200 ℃ and the pressure was gradually reduced to about 100 mbar over 6 hours, during which 298 g of distillate were collected. The mixture was stirred at a bottom temperature of 220 ℃ and a pressure of 60 mbar for a further 4 hours, during which a further 30 g of distillate were collected.

The viscosity of the resulting product at room temperature is so high (> 100000 mPa · s at 25 ℃) that further processing and use for the preparation of polyurethane foams is not possible.

2.2 one-pot Synthesis of anthranilic acid/trimellitic anhydride/glutaric acid (not according to the invention)

In the presence of a mechanical stirrer, a heating cover and a bottom temperatureA2 liter four necked round bottom flask with a nitrogen connection, diaphragm pump vacuum connection and 40cm packed column with column head and an intensive condenser was pre-charged with 349 grams of diethylene glycol (3.29 moles) while passing nitrogen. 192 g of trimellitic anhydride (1.00 mol) and 137 g of anthranilic acid (1.00 mol) were added thereto and the reaction mixture was stirred at a bottom temperature of 150 ℃ for 4 hours. Technical grade glutaric acid (134 g, 1.00 mol) was added and the reaction mixture was heated to a bottom temperature of 200 ℃ over 2 hours, during which water was distilled off. 15 mg of SnCl was added₂·2H₂O and the mixture was stirred under vacuum at a bottom temperature of 210 ℃ for 43 hours. 45 g of diethylene glycol (0.42 mol) were added and the mixture was stirred under vacuum at a bottom temperature of 200 ℃ for a further 5 hours. After cooling, the following properties of the polyester were determined:

hydroxyl number (mg KOH/g) 198

Acid value (mg KOH/g) 1.2

Viscosity (mPas at 25 ℃) No./> 50000

Viscosity (mPas at 50 ℃) 4050.

2.3 one-pot Synthesis of anthranilic acid/phthalic anhydride/adipic acid (method of the invention)

A4 liter four neck round bottom flask equipped with a mechanical stirrer, heating mantle, bottom thermometer, nitrogen connection, diaphragm pump vacuum connection, and a 40cm packed column with column cap and an intensive condenser was pre-charged with 849 grams of diethylene glycol (8.00 moles) while passing nitrogen through. 296 g of phthalic anhydride (2.00 mol) and 274 g of anthranilic acid (2.00 mol) were added thereto and the reaction mixture was stirred at a bottom temperature of 150 ℃ for 3 hours. After cooling to a bottom temperature of 110 ℃, adipic acid (587 g, 4.02 mol) was added and the reaction mixture was heated to a bottom temperature of 200 ℃ over 2 hours, during which water was distilled off. 36 mg of SnCl was added₂·2H₂O and the mixture is stirred under vacuum at a bottom temperature of 200 to 210 ℃ for 66 hours. After cooling, the following properties of the polyester were determined:

hydroxyl number (mg KOH/g) 177

Acid value (mg KOH/g) 2.0

Viscosity (mPas at 25 ℃) 2330.

2.4 one-pot Synthesis of aspartic acid/phthalic anhydride/adipic acid (invention)

A2 liter four neck round bottom flask equipped with a mechanical stirrer, heating mantle, bottom thermometer, nitrogen connection, diaphragm pump vacuum connection, and 40cm packed column with column head and an intensive condenser was preloaded with 497 grams of diethylene glycol (4.68 moles) while passing nitrogen. 148 g phthalic anhydride (1.00 mol) and 133 g aspartic acid (1.00 mol) were added thereto and the reaction mixture was stirred at a bottom temperature of 150 ℃ for 4.5 hours. After cooling to a bottom temperature of 120 ℃, adipic acid (292 g, 2.00 mol) was added and the reaction mixture was heated to a bottom temperature of 200 ℃ over 1.5 hours, during which water was distilled off. 19 mg of SnCl was added₂·2H₂O and the mixture was stirred under vacuum at a bottom temperature of 200 ℃ for 19 hours. After cooling, the following properties of the polyester were determined:

hydroxyl number (mg KOH/g) 180

Acid value (mg KOH/g) 2.0

Viscosity (mPas at 25 ℃) 4600.

2.5 one-pot Synthesis, glutamic acid/phthalic anhydride/adipic acid (method of the invention)

A2 liter four necked round bottom flask equipped with a mechanical stirrer, heating mantle, bottom thermometer, nitrogen connection, diaphragm pump vacuum connection and a 40cm packed column with column head and an intensive condenser was pre-charged with 500 grams of diethylene glycol (4.71 moles) while passing nitrogen. 148 g phthalic anhydride (1.00 mol) and 147 g glutamic acid (1.00 mol) were added thereto and the reaction mixture was stirred at a bottom temperature of 150 ℃ for 2.5 hours. After cooling to a bottom temperature of 120 ℃, adipic acid (292 g, 2.00 mol) was added and the reaction mixture was heated to a bottom temperature of 200 ℃ over 2 hours, during which water was distilled off. 19 mg of SnCl was added₂·2H₂O and the mixture was stirred under vacuum at a bottom temperature of 200 ℃ for 25 hours. 47 g of diethylene glycol (0.44 mol) are added andthe mixture was stirred under vacuum at a bottom temperature of 200 ℃ for a further 15 hours. After cooling, the following properties of the polyester were determined:

hydroxyl number (mg KOH/g) 202

Acid value (mg KOH/g) 0.8

Viscosity (mPas at 25 ℃) 2350.

2.6 one-pot Synthesis, glutamic acid/phthalic anhydride (method of the invention)

A2 liter four necked round bottom flask equipped with a mechanical stirrer, heating mantle, bottom thermometer, nitrogen connection, diaphragm pump vacuum connection, and a 40cm packed column with column head and an intensive condenser was pre-charged with 502 grams of diethylene glycol (4.73 moles) while passing nitrogen. 305 g phthalic anhydride (2.06 mol) and 304 g glutamic acid (2.07 mol) were added thereto and the reaction mixture was stirred at a bottom temperature of 150 ℃ for 2.5 hours. The reaction mixture was heated over 2 hours to a bottom temperature of 210 ℃ during which time water was distilled off. 20 mg of SnCl was added₂·2H₂O and the mixture was stirred under vacuum at a bottom temperature of 180 ℃ and 210 ℃ for 2 hours. 98 g of diethylene glycol (0.92 mol) were added and the mixture was stirred under vacuum at a bottom temperature of 200 ℃ and 210 ℃ for a further 11 hours. After cooling, the following properties of the polyester were determined:

hydroxyl number (mg KOH/g) 297

Acid value (mg KOH/g) 0.8

Viscosity (mPas at 25 ℃) 6500.

2.7 one-pot Synthesis, lysine/phthalic anhydride/glutaric acid (method of the invention)

A2 liter four necked round bottom flask equipped with a mechanical stirrer, heating mantle, bottom thermometer, nitrogen connection, diaphragm pump vacuum connection, and a 40cm packed column with column head and an intensive condenser was pre-charged with 400 grams of diethylene glycol (3.77 moles) while passing nitrogen. 355 g of phthalic anhydride (2.40 mol) and 176 g of lysine (1.20 mol) were added thereto and the reaction mixture was stirred at a bottom temperature of 150 ℃ for 2.5 hours. Technical grade glutaric acid (178 g, 1.33 mol) was added and the reaction was runThe mixture was heated to a bottom temperature of 200 ℃ over 2 hours, during which water was distilled off. 20 mg of SnCl was added₂·2H₂O and the mixture was stirred under vacuum at a bottom temperature of 200 ℃ for 16 hours. After cooling, the following properties of the polyester were determined:

hydroxyl number (mg KOH/g) 182

Acid value (mg KOH/g) 0.5

Viscosity (mPas at 25 ℃) of 17000.

3. Rigid polyurethane foam

Polyurethane rigid foams were prepared from the above-mentioned polyesterols having an OH number of from 150 to 250 according to the following general procedure. All parts are parts by weight:

L 2830	12 portions of
		Polyester (OH number 150-	73 parts of
TCPP	15 portions of
		B 8443	3 portions of
Water (W)	0.8 portion of
		DB	1.7 parts of
1792	2.8 parts of
N-pentane	About 13.4 parts
44V70L	About 200 parts

The exact amount of isocyanate V70L was calculated to achieve an index of 350 (100 x molar ratio of NCO groups to NCO-reactive groups).

The polyol, stabilizer, water, flame retardant and catalyst were stirred for 60 s at 1000 rpm using a Pendraulik stirrer. N-pentane was added and homogenized at 500-. The isocyanate was added and stirred at 4200 rpm for 10 s. The mixture was poured into a paper mold and allowed to react to completion. After storage at room temperature overnight, the rigid foam was sawn and analyzed.

Comparative standard polyesters were prepared from glutaric acid and ethylene glycol (OH number 216, viscosity at 25 ℃ 1980 mPas).