CN111518266B - Polyester polyol and preparation method and application thereof - Google Patents
Polyester polyol and preparation method and application thereof Download PDFInfo
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- CN111518266B CN111518266B CN202010548893.9A CN202010548893A CN111518266B CN 111518266 B CN111518266 B CN 111518266B CN 202010548893 A CN202010548893 A CN 202010548893A CN 111518266 B CN111518266 B CN 111518266B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4684—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Polyesters Or Polycarbonates (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to polyester polyol and a preparation method and application thereof, wherein the preparation raw materials of the polyester polyol comprise the following components in parts by mole: A) 100 parts by mole of acid anhydride and/or dicarboxylic acid; B) 0-110 mol portions of dihydric alcohol without phosphorus; C) 10-130 parts of phosphorus-containing dihydric alcohol. The polyester polyol provided by the invention has excellent flame retardant performance, the flame retardant is not easy to migrate, the durability is good, and meanwhile, the polyurethane prepared from the polyester polyol provided by the invention has excellent application performance.
Description
Technical Field
The invention relates to the technical field of polyester polyol, in particular to polyester polyol and a preparation method and application thereof, and particularly relates to polyester polyol with flame retardant property and a preparation method and application thereof.
Background
The polyester polyol is applied to preparation of polyurethane products such as elastomers, adhesives, sealing elements, coatings, hard bubbles, soft bubbles and the like, and has wide terminal application. Among them, many polyurethane products have high requirements for flame retardant properties, such as cables, building coatings, thermal insulation rigid foams, and the like.
The traditional method for preparing the flame-retardant polyurethane product is to add the flame retardant into the material in a physical blending mode, and no chemical bond exists between the flame retardant and the material. Therefore, the flame retardant has mobility, and the flame retardant performance of the product is reduced with the passage of time; in addition, the addition of flame retardants can lead to deterioration of the mechanical properties of the articles. The flame retardant generally contains halogen, phosphorus, nitrogen and the like, and the halogen-containing flame retardant generates toxic substances during combustion, thereby being harmful to human health and polluting the environment. In contrast, the flame retardant containing phosphorus is more environment-friendly and is one of the development trends of the flame retardant.
CN109134802A discloses a flame-retardant polyester polyol and a preparation method and application thereof, wherein the flame-retardant polyester polyol is prepared from the following raw materials in parts by weight: 100 parts of small-molecular organic dihydric alcohol, 80-150 parts of adipic acid, 10-30 parts of phosphoric acid, 0.1-0.5 part of catalyst and 300-700 parts of trimethylbenzene; wherein the trimethylbenzene is a water-carrying agent. The flame-retardant polyester polyol disclosed by the invention has the advantages that the flame-retardant element phosphorus is linked to the polyester polyol main chain through a reaction, the problem of phosphorus element migration is avoided, the use amount of the flame-retardant element is reduced, and the strength of a matrix is maintained. However, in the invention, the reaction can be smoothly carried out only by adding a large amount of trimethylbenzene as an organic solvent to the raw materials for preparing the polyester polyol, so that the residual organic solvent is difficult to remove in the polyurethane product obtained in the later stage, and the practicability is poor.
CN201510032241 discloses a dicarboxylic acid flame retardant monomer (shown below) with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) as a side group, and a flame retardant polyester polyol is prepared from the monomer. However, the DOPO contains aromatic rings and parallel ring structures with higher rigidity, and the addition of the DOPO type flame retardant in the polyurethane material at high content can increase the hardness and brittleness of the material and reduce the flexibility, low-temperature resistance, elasticity and other properties of the material, so that the addition amount of the flame retardant in the polyurethane material is limited to a certain extent; in addition, the synthesis method of the patent needs to use a large amount of toxic xylene solvent as a dehydrating agent, and the synthesis process is not environment-friendly and has poor practicability.
In view of the above, there is a need in the art to develop a polyurethane with flame retardant properties or a raw material for preparing the same, while achieving excellent flame retardant properties, migration resistance, mechanical properties, safety and environmental friendliness.
Disclosure of Invention
The invention aims to provide a polyester polyol, in particular to a polyester polyol with flame retardant property, wherein the preparation raw material of the polyester polyol contains a reactive phosphorus flame retardant, so that the polyester polyol has safety and environmental protection property, can ensure that the flame retardant action of the polyester polyol and a polyurethane product has durability, and has excellent application performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides polyester polyol, which comprises the following components in parts by mole:
A) 100 mole parts of acid anhydride and/or dicarboxylic acid
B) 0-110 mole portions of dihydric alcohol without phosphor
C) 10-130 parts of phosphorus-containing dihydric alcohol.
In the present invention, the content of component B (excluding the phosphorus diol) is 0 to 110 parts by mole, for example, 10 parts by mole, 20 parts by mole, 30 parts by mole, 40 parts by mole, 50 parts by mole, 60 parts by mole, 70 parts by mole, 80 parts by mole, 90 parts by mole, 100 parts by mole, 110 parts by mole, or the like.
In the present invention, the content of component C (phosphorus-containing diol) is 10 to 130 parts by mole, for example, 10 parts by mole, 20 parts by mole, 30 parts by mole, 40 parts by mole, 50 parts by mole, 60 parts by mole, 70 parts by mole, 80 parts by mole, 90 parts by mole, 100 parts by mole, 110 parts by mole, 120 parts by mole, 130 parts by mole, or the like.
The phosphorus-containing dihydric alcohol is added into the preparation raw materials of the polyester polyol, is used as a phosphorus-series reaction type flame retardant, has safety and environmental protection, is introduced into the molecular structure of the polyester polyol through the chemical bond effect, can ensure that the polyester polyol and a polyurethane product have excellent flame retardant performance, the flame retardant is not easy to migrate, and has good durability.
In addition, no organic solvent is added into the raw materials for preparing the polyester polyol, so that the obtained polyester polyol or polyurethane product has no solvent residue, low content of Volatile Organic Compounds (VOC) and strong practicability.
Preferably, the raw materials for preparing the polyester polyol do not contain organic solvents (such as xylene, trimethylbenzene and the like).
Preferably, the phosphorus-free glycol is present in an amount of 35 to 100 parts by mole.
The invention further preferably does not contain the content of the phosphorus diol, and the flame retardance, the migration resistance and the mechanical property of the material can be further improved within the content range.
Preferably, the content of the phosphorus-containing glycol is 20 to 80 molar parts.
The content of the phosphorus-containing dihydric alcohol is further optimized, and the flame retardance and the mechanical property of the material can be further improved within the content range.
Preferably, the preparation raw materials of the polyester polyol comprise the following components in parts by mole:
A) 100 mole parts of acid anhydride and/or dicarboxylic acid
B) 35-100 mol portions of dihydric alcohol without phosphorus
C) 20-80 mol portions of phosphorus-containing dihydric alcohol.
Preferably, the molar ratio of the raw materials for preparing the polyester polyol, C/(B + C), is greater than or equal to 5%, such as 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, etc., preferably greater than or equal to 20%, and more preferably greater than or equal to 50%. C/(B + C) refers to the percentage of moles of component C to the total moles of components B and C.
Preferably, the molar ratio of the raw materials for preparing the polyester polyol (B + C)/A is more than or equal to 100 percent, such as 110 percent, 120 percent, 130 percent, 140 percent, 150 percent, 160 percent, 170 percent, 180 percent, 190 percent, 200 percent and the like. (B + C)/A means the total moles of components B and C as a percentage of the moles of component A.
Preferably, the phosphorus-containing diol has a structure shown in formula I;
in the formula I, R is1Selected from C1-C25 alkyl, C1-C25 alkoxy, C6-C30 aryl or heteroaryl, at least one hydrogenAny one of a C1-C25 alkyl group in which atoms are substituted with halogen, a C1-C25 alkoxy group in which at least one hydrogen atom is substituted with halogen, or a C6-C30 aryl or heteroaryl group in which at least one hydrogen atom is substituted with halogen;
in the formula I, R is2And R3Each independently selected from the group consisting of C1-C25 alkylene, C6-C30 arylene or heteroarylene, C1-C25 alkylene in which at least one hydrogen atom is substituted by halogen, and C6-C30 arylene or heteroarylene in which at least one hydrogen atom is substituted by halogen;
the phosphorus-containing dihydric alcohol with the structure shown in the formula I is preferably selected, the content of phosphorus in the compound is higher, and the main body of the structure is chain-shaped and is matched with a specific formula, so that the synthesized polyester polyol and polyurethane have excellent flame retardance and mechanical property.
In the present invention, "C1 to C25" in the "C1 to C25 alkyl group" means the number of carbon atoms in the alkyl group and is a positive integer, and C1 to C25 alkyl groups mean C1 to C25 alkyl groups which are not substituted with other atoms or groups of atoms, and the same meanings apply to the same expressions.
In the present invention, halogen includes, but is not limited to, fluorine, chlorine, bromine, iodine, and the like.
Preferably, in formula I, R is1Is selected from any one of methyl, ethyl, propyl, isopropyl, phenyl, benzyl or at least one halogen substituted phenyl, preferably ethyl or phenyl.
Preferably, in formula I, R is2And R3Each independently selected from any one of ethylene, propylene or hexylene, preferably ethylene.
Preferably, the phosphorus-containing diol is selected from any one or two of the following compounds in combination:
preferably, the preparation method of the phosphorus-containing diol shown in the formula I comprises the following steps:
under the protection of nitrogen, under the action of a solvent (preferably tetrahydrofuran THF) and an alkali liquor (preferably n-butyl lithium or sodium hydroxide, wherein the amount of the alkali liquor is 2.1-2.4 times of the molar amount of the alkyl phosphorus dichloride and is not more than the molar amount of the dihydric alcohol monobenzyl ether), the alkyl phosphorus dichloride and the dihydric alcohol monobenzyl ether (the amount of the alkyl phosphorus dichloride is 2.2-2.5 times of the molar amount of the alkyl phosphorus dichloride) are subjected to substitution reaction to prepare an intermediate product. The intermediate product is fully reacted in the presence of a solvent (preferably tetrahydrofuran THF) and a palladium-carbon catalyst (the dosage is 5 to 20 percent of the molar weight of the intermediate product) in a hydrogen atmosphere, and the product is purified by column chromatography to obtain the dihydric alcohol containing phosphorus. The reaction process is as follows:
in addition to the above-mentioned methods, those skilled in the art can prepare the phosphorus-containing glycol by other conventional technical means, and the phosphorus-containing glycol can be obtained commercially.
Preferably, the acid anhydride comprises C4-C20 acid anhydride and/or C4-C20 acid anhydride in which at least one hydrogen atom is substituted by halogen, preferably any one or at least two combinations of aliphatic acid anhydride, aliphatic acid anhydride in which at least one hydrogen atom is substituted by halogen, aromatic acid anhydride in which at least one hydrogen atom is substituted by halogen, and further preferably phthalic anhydride.
Preferably, the dicarboxylic acid comprises a C3-C20 dicarboxylic acid and/or a C3-C20 dicarboxylic acid in which at least one hydrogen atom is substituted by halogen, preferably any one or at least two combinations of an aliphatic dicarboxylic acid, an aliphatic dicarboxylic acid in which at least one hydrogen atom is substituted by halogen, an aromatic dicarboxylic acid, and an aromatic dicarboxylic acid in which at least one hydrogen atom is substituted by halogen, more preferably any one or at least two combinations of adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, or isophthalic acid, and still more preferably any one or at least two combinations of adipic acid, sebacic acid, terephthalic acid, or isophthalic acid.
Preferably, the component a comprises a dicarboxylic acid, preferably adipic acid.
Preferably, the dihydric alcohol without phosphorus comprises C2-C20 dihydric alcohol without phosphorus, preferably any one or at least two combinations of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, nonanediol, diethylene glycol or triethylene glycol, further preferably any one or at least two combinations of ethylene glycol, 1, 4-butanediol or 1, 6-hexanediol, and further preferably 1, 4-butanediol.
Preferably, the raw materials for preparing the polyester polyol further comprise a catalyst, wherein the catalyst comprises one or at least two of antimony-based, titanium-based, germanium-based or tin-based catalysts, and preferably any one or at least two of antimony acetate, antimony trioxide, ethylene glycol antimony, tetraisobutyl titanate, tetraisopropyl titanate, germanium dioxide, stannous chloride, tin acetate or butyltin hydroxide.
Preferably, the catalyst comprises a titanium-based catalyst.
Preferably, the catalyst is used in an amount of specifically 0 to 600ppm, such as 50ppm, 100ppm, 150ppm, 200ppm, 250ppm, 300ppm, 350ppm, 400ppm, 450ppm, 500ppm, 550ppm, etc., preferably 40 to 300ppm, based on the total mass of components A, B and C.
Preferably, the hydroxyl value of the polyester polyol is 10-112 mg KOH/g, such as 15mg KOH/g, 20mg KOH/g, 25mg KOH/g, 30mg KOH/g, 35mg KOH/g, 40mg KOH/g, 45mg KOH/g, 50mg KOH/g, 55mg KOH/g, 60mg KOH/g, 65mg KOH/g, 70mg KOH/g, 75mg KOH/g, 80mg KOH/g, 85mg KOH/g, 90mg KOH/g, 95mg KOH/g, 100mg KOH/g, etc., preferably 22-112 mg KOH/g, and more preferably 37-112 mg KOH/g.
Preferably, the acid value of the polyester polyol is 0.01 to 10mg KOH/g, such as 0.1mg KOH/g, 0.5mg KOH/g, 1mg KOH/g, 1.5mg KOH/g, 2mg KOH/g, 2.5mg KOH/g, 3mg KOH/g, 3.5mg KOH/g, 4mg KOH/g, 4.5mg KOH/g, 5mg KOH/g, 5.5mg KOH/g, 6mg KOH/g, 6.5mg KOH/g, 7mg KOH/g, 7.5mg KOH/g, 8mg KOH/g, 8.5mg KOH/g, 9mg KOH/g, 9.5mg KOH/g, etc., preferably 0.01 to 5mg KOH/g, and further preferably 0.01 to 0.5mg KOH/g.
The second object of the present invention is to provide a method for producing the polyester polyol according to the first object, comprising: and mixing the component A, the component B and the component C according to the formula amount, and carrying out melt polycondensation to obtain the polyester polyol.
Preferably, the preparation method of the polyester polyol comprises the following steps:
under the protection of nitrogen, mixing the A, B and C, heating to 130-180 ℃ (for example, 140 ℃, 150 ℃, 160 ℃, 170 ℃ and the like), reacting at constant temperature for 1-5 h (for example, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h and the like), further heating to 180-220 ℃ (190 ℃, 200 ℃, 210 ℃ and the like), reacting at constant temperature, starting vacuum, and continuing to react until the acid value and the hydroxyl value are qualified; and (5) lowering, discharging and packaging.
The invention also aims to provide a polyurethane product, and the preparation raw material of the polyurethane product comprises the polyester polyol.
Preferably, the polyurethane article comprises a polyurethane elastomer, an adhesive, a seal, a coating, a hard or soft foam.
Preferably, the polyurethane article is a flame retardant polyurethane article.
Preferably, the polyurethane article is applied to a cable, film, architectural coating, or protective apparel coating.
Preferably, the raw materials for preparing the polyurethane product also comprise diisocyanate and a chain extender.
Preferably, the product raw materials of the polyurethane product can selectively comprise functional additives such as an antioxidant, a hydrolysis resistance agent, an anti-aging agent, a filler, a coloring agent and the like.
Compared with the prior art, the invention has the following beneficial effects:
the polyester polyol provided by the invention has excellent flame retardant performance, the flame retardant is not easy to migrate, the durability is good, and a polyurethane product prepared from the polyester polyol has excellent application performance, such as mechanical performance, flexibility, low temperature resistance, elasticity and the like. The flame retardant grade of the polyurethane elastomer can reach V1, even V0, is basically maintained after being placed in water at the constant temperature of 80 ℃ for 14 days, the tensile strength is 22.2-30.6 MPa, most of the tensile strength is over 23.0MPa, and the elongation at break is 500-620%.
In addition, the raw materials for preparing the polyester polyol do not need to be added with an organic solvent, so that the obtained polyester polyol or polyurethane product has no solvent residue, low content of Volatile Organic Compounds (VOC) and strong practicability.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The main raw materials used in the following preparation examples, comparative examples, application examples and comparative application examples are illustrated as follows: raw materials such as ethyl phosphorus dichloride, phenyl phosphine dichloride, butyl lithium, palladium carbon catalyst and the like are purchased from companies such as alpha chemical, Tokyo chemical and the like in the United states; ethylene glycol, diethylene glycol, 1, 4-butanediol (hereinafter may be simply referred to as butanediol), neopentyl glycol, hexanediol, and the like are available from BASF, and the like. The starting materials used are all commercially available, unless otherwise specified.
The acid value test method of the polyester polyol is referred to HG/T2709-.
The flame retardant performance test is referred to the UL94 standard.
The migration resistance test method comprises the following steps: the flame retardance of the material to be tested is tested by referring to UL94 standard after the material to be tested is placed in water with the constant temperature of 80 ℃ for 14 days.
Tensile strength and elongation at break test methods are referenced to ASTM D412.
In the present invention, eq. represents equivalent, and exemplarily, 2eq. represents 2 equivalent.
Preparation example 1
The preparation example provides a preparation method of dihydric alcohol containing phosphorus, which comprises the following specific steps:
(1) and (5) synthesizing an intermediate M.
Adding ethylene glycol monobenzyl ether Q (11.5mmol, 2.2eq.) into a dry 250mL three-neck round-bottom flask provided with a magnetic stirrer under the protection of nitrogen, and adding redistilled THF (60mL) for dissolving; cooling the system to-30 ℃ by using a liquid nitrogen acetone bath, and slowly dropwise adding at the temperaturenBuLi in tetrahydrofuran (1.0M, 11.0mmol, 2.1eq.) was added dropwise and the reaction was continued at this temperature for 10 minutes with stirring. At the temperature, adding a tetrahydrofuran (11mL) solution of ethyl phosphorus dichloride or phenyl phosphorus dichloride P (5.3mmol, 1.0eq.) into the system, and continuing stirring and reacting at the temperature for 30 minutes after the addition is finished; the liquid nitrogen acetone bath was removed and allowed to warm to room temperature naturally, and the reaction was continued with stirring until disappearance of the starting material was indicated by Thin Layer Chromatography (TLC) or nuclear magnetic monitoring. After the reaction is finished, cooling the system to 0 ℃, adding a saturated ammonium chloride solution (20mL) to quench the reaction, extracting the system with diethyl ether (20mL multiplied by 3 times), combining organic phases, washing with saturated saline solution, drying with anhydrous magnesium sulfate, decompressing to remove a solvent, and purifying a crude product by column chromatography (ethyl acetate/petroleum ether) to obtain a target product.
(2) And (3) synthesizing a target compound N.
In a 100mL three-necked round bottom flask with a magnetic stirrer and a suction head, the product M (10mmol, 1.0eq.) from the previous step and a palladium on carbon catalyst (1mmol, 10 mol%) were added sequentially, the system was replaced with hydrogen, tetrahydrofuran (50mL) was added, and the reaction was stirred at room temperature until disappearance of the starting material was detected by Thin Layer Chromatography (TLC). The solvent is removed under reduced pressure, and the crude product is purified by column chromatography (ethyl acetate/petroleum ether) to obtain a target product N.
Wherein R is1＝Et、R2＝CH2CH2The compound of (a) is designated as N1,1H NMR(400MHz，CDCl3)δ：0.93(t，3H)，1.40(q，2H)，3.45(t，2H)，3.66-3.73(m，2H)。
R1＝Ph、R2＝CH2CH2the compound of (a) is denoted as N2,1H NMR(400MHz，CDCl3)δ：3.45(t，2H)，3.68-3.75(m，2H),7.32(d，2H),7.40-7.45(m，3H)。
preparation example 2
Phosphorus-containing diol M1 was prepared according to the method disclosed in patent application CN109134802A and has the following structure:
examples 1 to 10, comparative example 1
The above examples and comparative examples provide different polyester polyols and were prepared as follows:
under the protection of nitrogen, the raw materials shown in the following table 1 are sequentially added into a reaction kettle; raising the temperature of the system to 140 ℃, and reacting at the constant temperature; when the acid value reaches 30mg KOH/g, the temperature is raised to 180 ℃, and the constant-temperature reaction is continued; and when the acid value is lower than 10mg KOH/g, raising the temperature of the system to 210 ℃, starting a vacuum system, slowly reducing the vacuum degree to-0.09 MPa within 0.5h, removing water and micromolecule alcohol in the system, stopping vacuum when the acid value and the hydroxyl value reach the standard, cooling and discharging. The indices of the polyester polyols obtained are shown in Table 2.
Comparative example 2
The polyester polyol was prepared by referring to the method of example 2 in patent CN110229322A, except that ethylene glycol and 1, 6-hexanediol were not added, wherein the addition amounts of butanediol, adipic acid and phosphoric acid were as shown in table 1, and the indices of the obtained polyester polyol are shown in table 2.
Comparative example 3
The polyester polyol prepared by the method of example 3 in patent CN104558570A is different in that butanediol is added and adipic acid is added, wherein the addition amounts of butanediol, adipic acid, DOPO and itaconic acid are shown in Table 1, and the indexes of the obtained polyester polyol are shown in Table 2.
Application examples 1 to 10, comparative application examples 1 to 3
The above application examples and comparative application examples provide different polyurethane elastomers (TPU) prepared as follows:
respectively and uniformly mixing the polyester polyol (30.0mol) prepared in examples 1-10 and comparative examples 1-3 with diphenylmethane diisocyanate (MDI) (32.0mol), adding 1, 4-Butanediol (BDO) (3.0mol) for chain extension, and stirring until the mixture fully reacts; then placing the mixture in a 120 ℃ oven for constant-temperature curing for 12 hours to obtain the polyurethane elastomer.
The results of the performance tests of application examples 1-10 and comparative application examples 1-3 are detailed in Table 2.
TABLE 1
TABLE 2
The data in Table 2 show that the polyurethane elastomer prepared from the polyester polyol provided by the invention has excellent flame retardant property, the flame retardant grade is V2 or above, most of the flame retardant grade is V1 grade, the highest flame retardant grade can reach V0 grade, the flame retardant property is durable, the flame retardant property of the product is basically unchanged after the product is placed in water at 80 ℃ for 14 days at constant temperature, the product has good mechanical property, the tensile strength is 22.2-30.6 MPa, most of the product is 23.0MPa or above, and the elongation at break is 500-620%.
The polyester polyol of comparative example 1 had no added phosphorous-containing diol, and the polyurethane elastomer had substantially no flame retardancy; as can be seen from comparison of example 5 and comparative example 2, the polyurethane elastomer prepared from the polyester polyol prepared by adding phosphoric acid in comparative example 2 has poor flame retardancy and elongation at break, while maintaining the same molar ratio of the flame retardant monomer to adipic acid; it can be seen from comparative example 5 and comparative example 3 that the polyurethane elastomer prepared by adding DOPO to the polyester polyol prepared in comparative example 3 has poor flame retardancy and elongation at break while maintaining the same molar ratio of the flame retardant monomer to adipic acid.
It can be seen from comparison between example 3 and example 10 that the invention can further improve the overall performance of the polyurethane elastomer by selecting the phosphorous-containing diol with a specific structure (example 3), because the phosphorous-containing diol of formula I has a suitable content of phosphorous element and a proper main structure, and can further optimize the product performance by matching with the specific formulation of the invention.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (35)
1. The polyester polyol is characterized in that the preparation raw materials of the polyester polyol comprise the following components in parts by mole:
A) 100 mole parts of acid anhydride and/or dicarboxylic acid
B) 0-110 mole portions of dihydric alcohol without phosphor
C) 10-130 parts by mole of phosphorus-containing dihydric alcohol;
the phosphorus-containing diol has a structure shown in formula I:
in the formula I, R is1Any one selected from C1-C25 alkyl, C1-C25 alkoxy, C6-C30 aryl or heteroaryl, C1-C25 alkyl with at least one hydrogen atom substituted by halogen, C1-C25 alkoxy with at least one hydrogen atom substituted by halogen, or C6-C30 aryl or heteroaryl with at least one hydrogen atom substituted by halogen;
in the formula ISaid R is2And R3Each independently selected from the group consisting of C1-C25 alkylene, C6-C30 arylene or heteroarylene, C1-C25 alkylene in which at least one hydrogen atom is substituted by halogen, and C6-C30 arylene or heteroarylene in which at least one hydrogen atom is substituted by halogen.
2. The polyester polyol according to claim 1, wherein the phosphorus-free diol is present in an amount of 35 to 100 parts by mole.
3. The polyester polyol according to claim 1, wherein the phosphorus-containing diol is contained in an amount of 20 to 80 parts by mole.
4. The polyester polyol according to any one of claims 1 to 3, wherein the molar ratio of the raw materials for preparing the polyester polyol C/(B + C) ≥ 5%.
5. The polyester polyol according to claim 4, wherein the molar ratio of the raw materials for preparing the polyester polyol, C/(B + C), is not less than 20%.
6. The polyester polyol according to claim 5, wherein the molar ratio of the raw materials for preparing the polyester polyol, C/(B + C), is not less than 50%.
7. The polyester polyol according to any one of claims 1 to 3, wherein the molar ratio of the raw materials for preparing the polyester polyol (B + C)/A is equal to or more than 100%.
8. The polyester polyol according to claim 1, wherein R in formula I1Is selected from any one of methyl, ethyl, propyl, isopropyl, phenyl, benzyl or phenyl substituted by at least one halogen.
9. The polyester polyol according to claim 1, wherein R is1Is ethyl or phenyl.
10. The polyester polyol according to claim 1, wherein R in formula I2And R3Each independently selected from any one of ethylene, propylene or hexylene.
11. The polyester polyol according to claim 1, wherein R is2And R3Is an ethylene group.
12. The polyester polyol according to claim 1, wherein the phosphorus-containing diol is selected from any one or two of the following compounds in combination:
13. the polyester polyol according to any one of claims 1 to 3, wherein the acid anhydride comprises C4 to C20 acid anhydride and/or C4 to C20 acid anhydride in which at least one hydrogen atom is substituted with halogen.
14. The polyester polyol according to claim 1, wherein the acid anhydride comprises any one of an aliphatic acid anhydride, an aliphatic acid anhydride in which at least one hydrogen atom is substituted with a halogen, an aromatic acid anhydride in which at least one hydrogen atom is substituted with a halogen, or a combination of at least two thereof.
15. The polyester polyol of claim 1, wherein the anhydride comprises phthalic anhydride.
16. The polyester polyol according to claim 1, wherein the dicarboxylic acid comprises a C3-C20 dicarboxylic acid and/or a C3-C20 dicarboxylic acid in which at least one hydrogen atom is substituted with a halogen.
17. The polyester polyol according to claim 1, wherein the dicarboxylic acid comprises any one of an aliphatic dicarboxylic acid, an aliphatic dicarboxylic acid in which at least one hydrogen atom is substituted with halogen, an aromatic dicarboxylic acid in which at least one hydrogen atom is substituted with halogen, or a combination of at least two thereof.
18. The polyester polyol according to claim 1, wherein the dicarboxylic acid comprises any one or a combination of at least two of adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid or isophthalic acid.
19. The polyester polyol according to claim 1, wherein the dicarboxylic acid comprises any one or a combination of at least two of adipic acid, sebacic acid, terephthalic acid, or isophthalic acid.
20. The polyester polyol according to claim 1, wherein the component a comprises a dicarboxylic acid.
21. The polyester polyol according to claim 1, wherein the component a comprises adipic acid.
22. The polyester polyol according to any one of claims 1 to 3, wherein the phosphorus-free diol comprises C2 to C20 phosphorus-free diol.
23. The polyester polyol according to claim 1, wherein the phosphorus-free diol comprises any one or a combination of at least two of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, nonanediol, diethylene glycol, or triethylene glycol.
24. The polyester polyol according to claim 1, wherein the phosphorus-free diol comprises any one or a combination of at least two of ethylene glycol, 1, 4-butanediol, or 1, 6-hexanediol.
25. The polyester polyol of claim 1, wherein the phosphorus-free diol comprises 1, 4-butanediol.
26. The polyester polyol according to any one of claims 1 to 3, wherein the hydroxyl value of the polyester polyol is 10 to 112mg KOH/g.
27. The polyester polyol according to claim 1, wherein the hydroxyl value of the polyester polyol is 22 to 112mg KOH/g.
28. The polyester polyol according to claim 1, wherein the hydroxyl value of the polyester polyol is 37 to 112mg KOH/g.
29. The polyester polyol according to claim 1, wherein the acid value of the polyester polyol is 0.01 to 10mg KOH/g.
30. The polyester polyol according to claim 1, wherein the acid value of the polyester polyol is 0.01 to 5mg KOH/g.
31. The polyester polyol according to claim 1, wherein the acid value of the polyester polyol is 0.01 to 0.5mg KOH/g.
32. A method for preparing the polyester polyol according to any one of claims 1 to 31, wherein the method comprises: and mixing the component A, the component B and the component C according to the formula amount, and carrying out melt polycondensation to obtain the polyester polyol.
33. A polyurethane article characterized in that a raw material for producing the polyurethane article comprises the polyester polyol according to any one of claims 1 to 31.
34. A polyurethane article as claimed in claim 33, wherein the polyurethane article comprises a polyurethane elastomer, an adhesive, a seal, a coating, a rigid or a flexible foam.
35. A polyurethane article according to claim 33, wherein said polyurethane article is a flame retardant polyurethane article.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4803230A (en) * | 1986-11-28 | 1989-02-07 | Montedipe S.P.A. | Polyols-polyesters and use thereof in the production of polyurethane foams |
| CN104004171A (en) * | 2014-06-16 | 2014-08-27 | 旭川化学（苏州）有限公司 | Preparation method of phosphorus-containing halogen-free environmentally-friendly flame-retardant polyester polyol |
| CN109134802A (en) * | 2017-06-27 | 2019-01-04 | 万华化学集团股份有限公司 | A kind of phosphor-containing halogen-free flame retardant thermoplastic polyurethane elastomer composition and its preparation method and application |
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| DE102013204550A1 (en) * | 2013-03-15 | 2014-09-18 | Evonik Industries Ag | Use of polyesters with inherent flame retardancy in adhesives and sealants |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4803230A (en) * | 1986-11-28 | 1989-02-07 | Montedipe S.P.A. | Polyols-polyesters and use thereof in the production of polyurethane foams |
| CN104004171A (en) * | 2014-06-16 | 2014-08-27 | 旭川化学（苏州）有限公司 | Preparation method of phosphorus-containing halogen-free environmentally-friendly flame-retardant polyester polyol |
| CN109134802A (en) * | 2017-06-27 | 2019-01-04 | 万华化学集团股份有限公司 | A kind of phosphor-containing halogen-free flame retardant thermoplastic polyurethane elastomer composition and its preparation method and application |
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