CN113929888B - Dimer acid polyester polyol and preparation method and application thereof - Google Patents

Dimer acid polyester polyol and preparation method and application thereof Download PDF

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CN113929888B
CN113929888B CN202111226662.7A CN202111226662A CN113929888B CN 113929888 B CN113929888 B CN 113929888B CN 202111226662 A CN202111226662 A CN 202111226662A CN 113929888 B CN113929888 B CN 113929888B
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dimer acid
polyester polyol
acid polyester
weight
parts
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CN113929888A (en
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赵波峰
蒋红梅
宋海峰
唐劲松
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Shanghai Huafon New Material Research & Development Technology Co ltd
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Shanghai Huafon New Material Research & Development Technology Co ltd
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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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/68—Unsaturated polyesters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention provides a dimer acid polyester polyol and a preparation method and application thereof, wherein the preparation raw materials of the dimer acid polyester polyol comprise 10-50 parts by weight of dihydric alcohol, 50-100 parts by weight of dimer acid, 0.005-0.05 part by weight of catalyst and 0.002-0.3 part by weight of composite stabilizer; by adding the composite stabilizer into the preparation raw materials, the risk of oxidization of dihydric alcohol in the esterification stage can be effectively reduced, and the risk of oxidization of dimeric acid in the polycondensation stage can be reduced, so that the side reaction in the whole preparation process is reduced, the acid value of the finally prepared polyol is lower, the molecular weight distribution is narrower, and the polyol is more suitable for being used as a synthesis raw material of aqueous polyurethane resin.

Description

Dimer acid polyester polyol and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to dimer acid polyester polyol, and a preparation method and application thereof.
Background
Polyurethane is one of the processes of rapid development of modern chemical industry, various polyurethane materials are continuously emerging, and the polyurethane materials are widely applied to aspects of food packaging, medical equipment, leather bags, shock absorbers, sealing devices, insulators and the like. The raw materials for preparing polyurethane are generally polyalcohol, chain extender, isocyanate and the like. Among these, the polyol has a decisive effect on the properties of polyurethane, and the polyol has a great influence on the properties of polyurethane, such as modulus, tensile strength, glass transition temperature, yellowing resistance and the like. The conventional polyester polyol, such as polybutylene adipate and polyethylene glycol adipate, has the defects in the aspects of hydrolysis resistance, oxidation resistance, ultraviolet decomposition resistance and the like, and influences the application of polyurethane in low-temperature resistant elastomers, anticorrosive paint, marine coating and the like with special requirements.
In all dicarboxylic acids, the molecular structure of dimer acid is the most unique, the main chain is longer, the dimer acid contains 36 carbon atoms and 2 large alkyl branched chains, and the dimer acid is completely converted from biomass, so that the dimer acid is increasingly applied in the field of high polymer materials due to the unique molecular structure of the dimer acid; the polyester polyol with higher relative molecular mass is synthesized by taking dimer acid, short molecular diol and the like as raw materials, and the polyester polyol is used for synthesizing the aqueous polyurethane resin, and has good weather resistance, flexibility and higher mechanical strength.
CN103113560a discloses a preparation method of dimer acid type polyester polyol, which takes long-chain dimer acid of dibasic acid and dihydric alcohol as main raw materials, and carries out esterification polymerization under the action of an organic catalyst and nitrogen protection, and further carries out vacuum dehydration and monomer removal to obtain dimer acid type polyester polyol with acid value less than 1mgKOH/g and number average molecular weight of 1300-3000 and different specification types; the invention has the characteristics of easy process operation, high product yield, stable product quality and low operation cost.
CN10120529a discloses a dimer acid polyester polyol and a preparation method thereof, the acid value of the dimer acid polyester polyol is 0.5-4 mgKOH/g, the hydroxyl value is 60-500 mgKOH/g, the preparation method is convenient to operate, and the product performance is stable. The preparation method of the invention mainly comprises the steps of reacting dimer acid and polyalcohol in the presence of a catalyst and a water-carrying agent under the protection of nitrogen, finally evaporating small molecular substances under the condition of reduced pressure distillation, and cooling in a vacuum state to obtain light brown dimer acid polyester polyalcohol.
However, the yield of dimer acid polyester polyol synthesized in the prior art is still low, and the chromaticity and acid value are still to be further reduced, so that the dimer acid polyester polyol is more suitable for the synthesis of aqueous polyurethane resin.
Therefore, the synthesis of a dimer acid polyester polyol with low color and acid number, narrow molecular weight distribution and high yield is a technical problem which the person skilled in the art is urgent to solve.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide dimer acid polyester polyol, a preparation method and application thereof, wherein the preparation raw materials of the dimer acid polyester polyol comprise a combination of specific parts of dihydric alcohol, dimer acid, a catalyst and a compound stabilizer, and the dimer acid polyester polyol prepared by adopting the preparation raw materials has lower chromaticity and acid value, narrower molecular mass distribution and higher yield, and is more suitable for synthesizing aqueous polyurethane resin.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a dimer acid polyester polyol, which is prepared from the following raw materials in parts by weight:
wherein the dihydric alcohol may be 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, or the like.
The dimer acid may be 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight, or the like.
The catalyst may be 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, or 0.045 parts by weight, etc.
The compound stabilizer may be 0.005 parts by weight, 0.007 parts by weight, 0.009 parts by weight, 0.011 parts by weight, 0.013 parts by weight, 0.015 parts by weight, 0.017 parts by weight, 0.019 parts by weight, 0.02 parts by weight, 0.023 parts by weight, 0.026 parts by weight, 0.029 parts by weight, or the like.
The preparation raw materials of the dimer acid polyester polyol provided by the invention comprise the combination of specific parts of dihydric alcohol, dimer acid, a catalyst and a compound stabilizer; the production of byproducts in the whole preparation process of the dimer acid polyester polyol can be limited by adding a specific part of composite stabilizer into the preparation raw materials; the addition of the composite stabilizer can reduce the oxidation of the dihydric alcohol in the esterification stage on one hand; on the other hand, the oxidation of the dimer acid in the polycondensation stage can be reduced, so that less byproducts are generated in the whole preparation process, and the dimer acid polyester polyol with low acid value and low chromaticity is finally obtained; and the dimer acid polyester polyol prepared by combining the preparation raw materials has narrower molecular mass distribution and higher yield, so that the dimer acid polyester polyol is more suitable for synthesizing aqueous polyurethane resin.
The dimer acid can be selected from high-purity dimer acid of CRODA company in England, the mass fraction is more than 99%, and the structure is shown as formula I:
preferably, the glycol is a glycol having a carbon chain of less than 10 (e.g., 9, 8, 7, 6, 5, 4, 3, 2, or 1, etc.).
Preferably, the glycol comprises any one or a combination of at least two of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol or 1, 6-hexanediol.
Preferably, the catalyst comprises any one or a combination of at least two of tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, stannous octoate, dibutyltin dilaurate, bismuth laurate, zinc oxide or antimony trioxide.
Preferably, the content of the catalyst in the dimer acid polyester polyol is 0.01 to 0.012 parts by weight, for example 0.0102 parts by weight, 0.0104 parts by weight, 0.0106 parts by weight, 0.0108 parts by weight, 0.011 parts by weight, 0.0112 parts by weight, 0.0114 parts by weight, 0.0116 parts by weight, or 0.0118 parts by weight, etc.
Preferably, the composite stabilizer comprises a combination of a phosphate-based heat stabilizer and a phosphite-based thermo-oxidative stabilizer.
In the preferred technical scheme of the invention, phosphate heat stabilizer and phosphite ester thermo-oxidative stabilizer are matched to be used as composite stabilizer, so that the generation of byproducts can be reduced better.
Preferably, the mass ratio of the phosphate ester heat stabilizer to the phosphite ester heat stabilizer is 0.5-1:1, for example, 0.55:1, 0.6:1, 0.65:1, 0.7:1, 0.75:1, 0.8:1, 0.85:1, 0.9:1 or 0.95:1, etc.
As the preferable technical scheme of the invention, the mass ratio of the phosphate ester heat stabilizer to the phosphite ester thermo-oxidative stabilizer is 0.5-1:1, so that the generation of byproducts can be better reduced, on one hand, if the addition amount of the phosphate ester heat stabilizer is relatively high, the short molecular diol and dimer acid in the esterification stage can be oxidized, and the byproducts are generated to influence the chromaticity of the finally obtained polyol; on the other hand, if the amount of the phosphite type thermo-oxidative stabilizer to be added is relatively high, it may cause instability of the polyol in the polycondensation reaction stage, and further, it may cause a low yield of the finally produced polyol and a broad molecular weight distribution.
Preferably, the phosphate ester heat stabilizer comprises any one or a combination of at least two of triphenyl phosphate, triethyl methylphosphonate or triethyl phosphonoacetate.
Preferably, the phosphite thermo-oxidative stabilizer comprises any one or a combination of at least two of triphenyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, dioctadecyl pentaerythritol diphosphite or tetra (2, 4-di-tert-butylphenol) -4,4' -biphenylyl diphosphite.
Preferably, the dimer acid polyester polyol also comprises other dibasic acids in the preparation raw materials.
In the present invention, the term "other dibasic acid" refers to a dibasic acid excluding dimer acid; for example, the other dibasic acids may include any one or a combination of at least two of succinic acid, glutaric acid, adipic acid, azelaic acid or sebacic acid.
Preferably, the content of the other dibasic acid in the dimer acid polyester polyol is 0 to 50 parts by weight and not equal to 0, for example, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight or the like.
In a second aspect, the present invention provides a process for the preparation of dimer acid polyester polyol according to the first aspect, comprising the steps of:
(1) Reacting dihydric alcohol, dimeric acid, a compound stabilizer and optionally other dibasic acids to obtain an intermediate product;
(2) And (3) reacting the intermediate product obtained in the step (1) with a catalyst to obtain the dimer acid polyester polyol.
Preferably, the reactions of step (1) and step (2) are both carried out under inert gas.
Preferably, the inert gas comprises nitrogen.
Preferably, the reaction of step (1) comprises a combination of an initial reaction and an esterification dehydration reaction.
Preferably, the temperature of the initial reaction is 130 to 160 ℃, for example 133 ℃, 136 ℃, 139 ℃, 143 ℃, 146 ℃, 149 ℃, 153 ℃, 156 ℃, 159 ℃, or the like.
Preferably, the initial reaction time is 3 to 120min, for example, 5min, 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min or 110min, etc.
Preferably, the esterification and dehydration reaction is performed under a temperature-rising condition, and more preferably, under a constant temperature-rising condition.
As a preferable technical scheme, the invention adopts a uniform temperature rising mode to carry out esterification dehydration reaction, so that the yield of dimer acid polyester polyol can be improved.
Preferably, the rate of temperature rise is 5 to 30 ℃/h, for example 7 ℃/h, 9 ℃/h, 11 ℃/h, 13 ℃/h, 15 ℃/h, 17 ℃/h, 19 ℃/h, 21 ℃/h, 23 ℃/h, 25 ℃/h, 27 ℃/h or 29 ℃/h, etc.
Preferably, the temperature of the post-warming system is 210 to 250 ℃, for example 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, or the like.
Preferably, the time of the esterification dehydration reaction is 3 to 5 hours, for example, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours, or the like.
Preferably, the reaction in the step (2) further comprises a step of heat preservation.
Preferably, the temperature of the incubation is 210 to 250 ℃, e.g., 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, or the like.
Preferably, the time of the incubation is 30-180 min, for example 40min, 60min, 80min, 100min, 120min, 140min, 160min or 180min, etc.
Preferably, the reaction of step (2) is a reduced pressure distillation polycondensation reaction.
Preferably, the reduced pressure distillation polycondensation reaction is carried out for a period of time of 2 to 6 hours, for example, 2.4 hours, 2.8 hours, 3.2 hours, 3.6 hours, 4 hours, 4.4 hours, 4.8 hours, 5 hours, 5.2 hours, 5.6 hours, or the like.
Preferably, the pressure of the reduced pressure distillation polycondensation reaction is-0.1 to 0Mpa, for example-0.09 Mpa, -0.08Mpa, -0.07Mpa, -0.06Mpa, -0.05Mpa, -0.04Mpa, -0.03Mpa, -0.02Mpa, or-0.01 Mpa, etc.
Preferably, the dimer acid polyester polyol of step (2) has a hydroxyl number of 30 to 120mg KOH/g, for example 40mg KOH/g, 50mg KOH/g, 60mg KOH/g, 70mg KOH/g, 80mg KOH/g, 90mg KOH/g, 100mg KOH/g, 110mg KOH/g or 120mg KOH/g, etc.
Preferably, the dimer acid polyester polyol of step (2) has an acid number of 0.1 to 1mg KOH/g, for example 0.2mg KOH/g, 0.3mg KOH/g, 0.4mg KOH/g, 0.5mg KOH/g, 0.6mg KOH/g, 0.7mg KOH/g, 0.8mg KOH/g or 0.9mg KOH/g, etc.
As a preferable technical scheme, the preparation method comprises the following steps:
(1) Under the protection of inert gas, dihydric alcohol, dimer acid, a compound stabilizer and optionally other dibasic acids react for 3-120 min at 130-160 ℃, and the temperature is raised to 210-250 ℃ for esterification and dehydration reaction for 3-5 h under the condition of the temperature rising speed of 5-30 ℃/h, so as to obtain an intermediate product;
(2) Mixing the intermediate product obtained in the step (1) with a catalyst, preserving the temperature at 210-250 ℃ for 30-180 min, carrying out distillation polycondensation reaction for 2-6 h under the pressure of-0.1-0 Mpa, and obtaining the dimer acid polyester polyol with the hydroxyl value of 30-120 mgKOH/g and the acid value of 0.1-1 mgKOH/g.
In a third aspect, the present invention provides the use of a dimer acid polyester polyol as described in the first aspect in the synthesis of an aqueous polyurethane resin.
Compared with the prior art, the invention has the following beneficial effects:
the preparation raw materials of the dimer acid polyester polyol provided by the invention comprise the combination of specific parts of dihydric alcohol, dimer acid, a catalyst and a compound stabilizer; by adding the composite stabilizer into the raw materials, on one hand, the risk of oxidization of dihydric alcohol in the esterification stage can be reduced; on the other hand, the risk of oxidation of dimer acid in the polycondensation stage can be reduced, thereby reducing the generation of byproducts in the whole preparation process, and obtaining dimer acid polyester polyol with an acid value of less than 0.3mgKOH/g and a hydroxyl value of less than 150 mgKOH/g; and the dimer acid polyester polyol prepared by the preparation raw materials has narrower molecular mass distribution and higher yield, so that the dimer acid polyester polyol is more suitable for synthesizing aqueous polyurethane resin.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The dimer acid polyester polyol comprises the following raw materials in parts by weight:
the preparation method of the dimer acid polyester polyol provided by the embodiment comprises the following steps:
(1) Under the protection of nitrogen, adding ethylene glycol, dimer acid (with the molecular weight of 560), triethyl methylphosphonate and triphenyl phosphite into 2000mL of four-port round-bottom sesame seed cake provided with a heating sleeve, a magnetic stirrer, a temperature probe, a distillation head, a condensation reflux device and an ice salt bath cooling receiving bottle, introducing nitrogen and stirring for 15min, slowly heating to 160 ℃, heating to 250 ℃ under the condition of the heating speed of 5 ℃/h, and carrying out esterification dehydration reaction for 3-4 h to obtain an intermediate product with the acid value of less than 1.2 mgKOH/g;
(2) Mixing the intermediate product obtained in the step (1) with tetrabutyl titanate, heating to 230 ℃, preserving heat for 30min, carrying out distillation polycondensation reaction for 3h under the pressure of minus 0.095Mpa, and cooling to obtain the dimer acid polyester polyol.
Example 2
The dimer acid polyester polyol comprises the following raw materials in parts by weight:
the preparation method of the dimer acid polyester polyol provided by the embodiment comprises the following steps:
(1) Under the protection of nitrogen, dimer acid (molecular weight is 560), adipic acid, hexanediol, triethyl phosphonoacetate and triphenyl phosphite are added into 2000mL of four-port round bottom sesame seed cake provided with a heating sleeve, a magnetic stirrer, a temperature probe, a distillation head, a condensation reflux device and an ice salt bath cooling receiving bottle, nitrogen is introduced into the four-port round bottom sesame seed cake for stirring for 15min, the temperature is slowly raised to 160 ℃, the temperature is raised to 210 ℃ under the condition of the temperature raising speed of 5 ℃/h, and esterification dehydration reaction is carried out for 1-3 h, so that an intermediate product with the acid value less than 1.2mgKOH/g is obtained;
(2) Mixing the intermediate product obtained in the step (1) with tetrabutyl titanate, heating to 230 ℃, preserving heat for 30min, carrying out distillation polycondensation reaction for 3h under the pressure of minus 0.095Mpa, and cooling to obtain the dimer acid polyester polyol.
Example 3
The dimer acid polyester polyol comprises the following raw materials in parts by weight:
the preparation method is the same as in example 2.
Example 4
The dimer acid polyester polyol comprises the following raw materials in parts by weight:
the preparation method is the same as in example 2.
Example 5
The dimer acid polyester polyol comprises the following raw materials in parts by weight:
the preparation method is the same as in example 2.
Example 6
A dimer acid polyester polyol differing from example 1 only in that dimer acid was added in an amount of 80 parts by weight, and succinic acid was added in an amount of 20 parts by weight, and other components, amounts and preparation methods were the same as in example 1.
Example 7
A dimer acid polyester polyol differing from example 1 only in that triethyl methylphosphonate was added in an amount of 0.5 parts by weight and triphenyl phosphite was added in an amount of 0.13 parts by weight, and other components, amounts and preparation methods were the same as in example 1.
Example 8
A dimer acid polyester polyol differing from example 1 only in that triethyl methylphosphonate was added in an amount of 1 part by weight and triphenyl phosphite was added in an amount of 0.08 part by weight, and other components, amounts and preparation methods were the same as in example 1.
Comparative example 1
A dimer acid polyester polyol differing from example 1 only in that triethyl methylphosphonate and triphenyl phosphite were not added, and other components, amounts and preparation methods were the same as in example 1.
Comparative example 2
A dimer acid polyester polyol differing from example 5 only in that triethylphosphonoacetate and tris (2, 4-di-t-butylphenyl) phosphite were not added, and other components, amounts and preparation methods were the same as in example 1.
Comparative example 3
A dimer acid polyester polyol differing from example 1 in that triethyl methylphosphonate was not added and triphenyl phosphite was added in an amount of 0.18 parts by weight, and the other components, amounts and preparation methods were the same as in example 1.
Comparative example 4
A dimer acid polyester polyol differing from example 1 in that triphenyl phosphite was not added and triethyl methylphosphonate was added in an amount of 0.18 parts by weight, and the other components, amounts and preparation methods were the same as in example 1.
Performance test:
(1) Acid value: (1) accurately weighing 6-12 g of sample in a 250mL conical flask; (2) measuring 30mL of methanol solution of toluene in the conical flask, plugging a stopper, and performing ultrasonic treatment until the methanol solution is completely dissolved; (3) adding 2-3 drops of phenolphthalein indicator, and titrating with calibrated 0.1mol/L ethanol solution of potassium hydroxide until the solution is reddish, wherein the reddish is kept for 30 seconds and does not fade, namely the titration end point; (4) taking another 250mL conical flask, adding only 30mL of methanol solution of toluene without adding a sample, and repeating the step (3) for a blank test; (5) according to the calculation formula of the Acid Value (AV): av= (V-V) 0 ) XC X M/M; wherein V represents the dosage of ethanol solution of potassium hydroxide and mL when the sample is titrated; v (V) 0 Represents the dosage of ethanol solution of potassium hydroxide in blank test, mL; c represents the concentration of ethanol solution of potassium hydroxide and mol/L; m represents the molar mass, g/mol, of potassium hydroxide; m represents the weight of the sample, g.
(2) Hydroxyl number: (1) accurately weighing 3-6 g of sample in a 250mL conical flask; (2) accurately pipetting 5mL of acetylating reagent into the above conical flaskIn the process, a plug is plugged, ultrasonic treatment is carried out until the plug is completely dissolved, and then the plug is kept stand for 5min to enable the plug to completely react; (3) adding 2mL of distilled water into the conical flask, shaking uniformly, transferring 10mL of pyridine water solution, slowly adding the pyridine water solution into the conical flask to wash the wall of the conical flask, shaking uniformly, and standing for 5min; (4) adding 8-9 drops of phenolphthalein indicator, and titrating with a calibrated ethanol solution of 0.6mol/L potassium hydroxide until the solution is reddish, wherein the reddish is kept for 30 seconds and does not fade, namely the titration end point; (5) taking a 250mL conical flask without adding a sample, and repeating the steps (2), (3) and (4) for a blank test; (6) a formula for calculating the hydroxyl value (OHV) is ohv= (V) 0 V). Times.C.times.M/M; wherein V is 0 Represents the dosage of ethanol solution of potassium hydroxide in blank test, mL; v represents the dosage of ethanol solution of potassium hydroxide in titration of the sample, and mL; c represents the concentration of potassium hydroxide ethanol solution and mol/L; m represents the molar mass, g/mol, of potassium hydroxide; m represents the weight of the sample, g.
(3) Chromaticity: the test was carried out according to GB/T3143-1982 colour determination of liquid chemical products.
(4) Molecular weight distribution: the test was performed using gel permeation chromatography GPC from Waters, autosampler Waters 2707Autosampler, detector Waters 2414refractive Index Detector.
(5) Viscosity: the test was carried out according to the method provided in GB/T12008.8-1992.
(6) Yield: the calculation formula is M/M multiplied by 100%, M represents the mass of the dimer acid polyester polyol obtained by synthesis, and M represents the total mass of the raw materials required by synthesis.
The dimer acid polyester polyols obtained in examples 1 to 8 and comparative examples 1 to 4 were tested according to the above test methods, and the test results are shown in Table 1:
TABLE 1
From the data in table 1, it can be seen that: the dimer acid polyester polyol provided by the invention has the advantages of lower chromaticity, higher yield and narrower molecular weight distribution.
Specifically, the dimer acid polyester polyol obtained in examples 1 to 8 has a hydroxyl value of 28.2 to 62.3mgKOH/g; the acid value is 0.21-0.62 mgKOH/g; the yield is 84.1 to 86.4 percent; the viscosity is 83-560 cp/70 ℃; the chromaticity is 20-40; the molecular weight distribution is 1.62-2.0 Mw/Mn.
Comparative example 1 and comparative example 1, and comparative example 5 and comparative example 2, it was found that the dimer acid polyester polyol prepared without adding the composite stabilizer was lower in yield and higher in color, and also broader in molecular weight distribution.
As can be seen from comparative examples 1 and comparative examples 3 to 4, dimer acid polyester polyols prepared by adding only one stabilizer are also lower in yield, higher in chromaticity and wider in molecular weight distribution.
Further, it was found from a comparison of example 1 and examples 7 to 8 that the amount of any one of the compound stabilizers used was too large to affect the chromaticity, molecular weight distribution and yield of the dimer acid polyester polyol obtained, and that the dimer acid polyester polyol having the most excellent comprehensive properties could be obtained only in the preferable amount range.
The applicant states that the present invention is illustrated by the above examples as well as a process for preparing a dimer acid polyester polyol and its use, but the present invention is not limited to, i.e. it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (26)

1. The dimer acid polyester polyol is characterized by comprising the following raw materials in parts by weight:
the dihydric alcohol comprises any one or a combination of at least two of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol or 1, 6-hexanediol;
the compound stabilizer comprises a combination of a phosphate heat stabilizer and a phosphite thermo-oxidative stabilizer;
the mass ratio of the phosphate heat stabilizer to the phosphite ester heat-oxygen stabilizer is 0.5-1:1;
the hydroxyl value of the dimer acid polyester polyol is 28.2-62.3 mgKOH/g, the acid value is 0.21-0.62 mgKOH/g, the viscosity is 83-560 cp/70 ℃, the chromaticity is 20-40, and the molecular weight distribution is 1.62-2.0 Mw/Mn.
2. The dimer acid polyester polyol according to claim 1, characterized in that the catalyst comprises any one or a combination of at least two of tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, stannous octoate, dibutyltin dilaurate, bismuth laurate, zinc oxide or antimony trioxide.
3. The dimer acid polyester polyol according to claim 1, wherein the content of the catalyst in the raw material for producing the dimer acid polyester polyol is 0.01 to 0.012 parts by weight.
4. The dimer acid polyester polyol according to claim 1, characterized in that the phosphate ester heat stabilizer comprises any one or a combination of at least two of triphenyl phosphate, triethyl methylphosphonate or triethyl phosphonoacetate.
5. The dimer acid polyester polyol according to claim 1, characterized in that the phosphite based thermo-oxidative stabilizer comprises any one or a combination of at least two of triphenyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, dioctadecyl pentaerythritol diphosphite or tetrakis (2, 4-di-t-butylphenol) -4,4' -biphenyl diphosphite.
6. The dimer acid polyester polyol according to claim 1, characterized in that the preparation raw material of the dimer acid polyester polyol further comprises other dibasic acids.
7. The dimer acid polyester polyol according to claim 6, characterized in that the other dibasic acids comprise any one or a combination of at least two of succinic acid, glutaric acid, adipic acid, azelaic acid or sebacic acid.
8. The dimer acid polyester polyol according to claim 6, wherein the content of other dibasic acids in the raw material for producing the dimer acid polyester polyol is 0 to 50 parts by weight and not equal to 0.
9. A process for the preparation of dimer acid polyester polyol according to any of claims 1 to 8, characterized in that the process comprises the steps of:
(1) Reacting dihydric alcohol, dimeric acid, a compound stabilizer and optionally other dibasic acids to obtain an intermediate product;
(2) And (3) reacting the intermediate product obtained in the step (1) with a catalyst to obtain the dimer acid polyester polyol.
10. The process of claim 9, wherein the reactions of step (1) and step (2) are each carried out under inert gas.
11. The method of claim 10, wherein the inert gas comprises nitrogen.
12. The method of claim 10, wherein the reaction of step (1) comprises a combination of an initial reaction and an esterification dehydration reaction.
13. The method of claim 12, wherein the initial reaction temperature is 130 to 160 ℃.
14. The method of claim 12, wherein the initial reaction time is 3 to 120 minutes.
15. The production method according to claim 12, wherein the esterification dehydration reaction is performed at an elevated temperature.
16. The production method according to claim 15, wherein the esterification and dehydration reaction is carried out under a condition of a constant temperature rise.
17. The method according to claim 15, wherein the rate of temperature rise is 5 to 30 ℃/h.
18. The method according to claim 15, wherein the temperature of the system after the temperature rise is 210 to 250 ℃.
19. The method according to claim 12, wherein the time for the esterification and dehydration reaction is 3 to 5 hours.
20. The method of claim 9, wherein the reaction in step (2) is preceded by a step of incubating.
21. The method of claim 20, wherein the temperature of the incubation is 210-250 ℃.
22. The method according to claim 20, wherein the time for the heat preservation is 30 to 180 minutes.
23. The method according to claim 9, wherein the reaction in the step (2) is a reduced pressure distillation polycondensation reaction.
24. The process according to claim 23, wherein the reduced pressure distillation polycondensation reaction is carried out for a period of 2 to 6 hours.
25. The method according to claim 23, wherein the pressure of the reduced pressure distillation polycondensation reaction is from-0.1 to 0Mpa.
26. Use of the dimer acid polyester polyol according to any one of claims 1 to 8 in the synthesis of aqueous polyurethane resins.
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