CN112979930B - Preparation of high biomass polyester polyols from hydrogenated itaconic acid - Google Patents

Preparation of high biomass polyester polyols from hydrogenated itaconic acid Download PDF

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CN112979930B
CN112979930B CN201911292836.2A CN201911292836A CN112979930B CN 112979930 B CN112979930 B CN 112979930B CN 201911292836 A CN201911292836 A CN 201911292836A CN 112979930 B CN112979930 B CN 112979930B
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acid
polyester polyol
reaction
antioxidant
high biomass
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CN112979930A (en
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林永泰
苏琦钧
陈俊业
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Coating P Materials 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
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • 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

Abstract

The present invention relates to the preparation of high biomass polyester polyols from hydrogenated itaconic acid, and in particular to high biomass polyester polyols, especially those comprising hydrogenated itaconic acid (i.e., 2-methylsuccinic acid (2-mSA)). Compared with the prior biomass polyester polyol, the high biomass content polyester polyol provided by the invention accords with the APHA color specification and is beneficial to further application. The invention also relates to a process for preparing a high biomass polyester polyol.

Description

Preparation of high biomass polyester polyols from hydrogenated itaconic acid
Technical Field
The present invention relates to high biomass, especially polyester polyols containing hydrogenated itaconic acid, i.e., 2-methyl succinic acid (2-mSA). Compared with the prior biomass polyester polyol, the high biomass content polyester polyol provided by the invention accords with the APHA chromaticity (American public health Association chromaticity) specification, and can obtain polyurethane with good transparency, softness and high reverse elasticity when being further applied to the preparation of polyurethane. Also relates to a process for preparing high biomass polyester polyols.
Background
Petroleum is the most important energy source in the world, and petrochemical products are not known, and comprise small molecular compounds, polymers and the like, such as polyurethane and the like. The polyol required for preparing polyurethane is generally prepared by adopting dicarboxylic acid and dihydric alcohol through glycidyl ester. However, with the increase of global petroleum usage, petroleum reserves are decreasing year by year, and in terms of continuous development, replacement of petrochemical products with biomass resources is an essential direction of future industrial development, and some products in europe and america have begun to be commercialized.
While the prior art can prepare the biomass diol, most of the biomass dicarboxylic acid is linear dicarboxylic acid, and most of the prepared polyester polyol has crystallinity, so the development and application of the biomass polyurethane are greatly limited.
The common bio-dibasic acids in the market comprise succinic acid, 2-methyl succinic acid (2-mSA) and the like,
and it is known that 2-mSA can be prepared by fermentation using biomass glycerol or corn starch, and attempts have been made to solve the problems caused by the linear dibasic acid using 2-mSA as a reaction monomer. However, 2-mSA, which is produced from either petrochemical or biological sources, has a relatively high iron ion content, and it is difficult to produce polyester polyols having a desirable color (currently industry polyester polyol color specifications fall on the order of 40-100 APHA color or less) if 2-mSA is used in a polyester polyol formulation at a level of >30 mole%.
Accordingly, there remains a need for polyester polyols, particularly biopolyester polyols, that meet color requirements.
Disclosure of Invention
The present invention relates to the provision of polyester polyols which meet colour requirements and are of high biomass content, in particular of high content 2-mSA and colour <30APHA.
The invention also relates to a process for preparing said polyester polyol comprising the step of using a two-component antioxidant in the process.
Detailed Description
The invention is described in more detail in the following paragraphs. The aspects so described may be combined with any other aspect unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
In the context of the present invention, unless the context dictates otherwise, the terms used are interpreted in accordance with the following definitions.
As used herein, the singular forms "a," "an," and "the" include the singular and plural referents unless the context clearly dictates otherwise.
The term "comprising" as used herein is synonymous with "including" or "containing" and is inclusive or open-ended and does not exclude additional unrecited members, elements or method steps.
The recitation of numerical endpoints includes all numbers and fractions subsumed within that individual range, and that endpoint.
Unless otherwise defined, all terms (including technical and scientific terms) used to describe the invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. By way of further guidance, term definitions are included to better understand the teachings of the present invention.
The present invention relates to the provision of polyester polyols which meet colour requirements and are of high biomass content, in particular of high content 2-mSA and colour <30APHA.
High biomass polyester polyols
The polyester polyol is produced by esterification of a polyol with a polybasic acid, and the characteristics of the reactive monomer and the polyester polyol are described below.
Polyhydric alcohol
Polyol refers to hydrocarbon derivatives having two or more hydroxyl groups (-OH). In the present invention, for example, alkyl polyols, unsaturated or aromatic polyols may be used. Biomass polyols may also be used. As reactive monomers for polyester polyols. The number of hydroxyl groups in the hydrocarbon derivative may be clearly expressed, for example, dihydric alcohol, trihydric alcohol …, and the like.
In the present invention, it is preferable to use a (cyclo) alkyl diol as a reaction monomer. Examples of polyols include, but are not limited to, diols having 2 to 12 carbon atoms and 36 carbon atoms, such as one or more of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, 2-methyl-1, 3-propanediol, hexylene glycol, dipropylene glycol, butylethylpropanediol, diethylpentylene glycol, 3-methyl-1, 5-pentylene glycol, 1, 4-cyclohexyldimethanol, cyclohexanediol, dodecacylalkylene glycol, spiroglycol, trimethylpentylene glycol, pentylene glycol, hydroxypivalate neopentylglycol monoester, ethylhexanediol, dodecylene glycol, and the like, hydroquinone dihydroxyethyl ether, resorcinol dihydroxyethyl ether, trimethylolpropane, glycerol, trimethylolethane, 1,2, 6-hexanetriol, and the like. In one embodiment of the present invention, ethylene glycol and butanediol are used as reactive monomers; in one embodiment of the present invention, propylene glycol is used as the reactive monomer.
Polybasic acid
Polyacids refer to hydrocarbon derivatives having two or more carboxyl groups (-COOH). In the present invention, for example, alkyl polyacids, unsaturated or aromatic polyacids may be used. As reactive monomers for polyester polyols. The number of carboxyl groups carried by the hydrocarbon derivative, such as dibasic acid, tribasic acid …, etc., can also be clearly indicated.
In the present invention, it is preferable to use an alkyl dibasic acid as a reactive monomer, which at least comprises 2-methyl succinic acid (2-mSA) as a reactive monomer, and the soft segment of polyurethane exhibits preferable flexibility due to the side chain methyl group of the structure of 2-mSA. In addition, the side chain methyl increases the intermolecular distance, so that the steric hindrance is increased, and the regularity of the molecular chain is reduced. Thus, such a structure not only does not disrupt Tg, but also reduces Tm, imparting unique properties to polyester polyols for use in polyurethanes. Other biological monomers, such as biosuccinic acid, may also be used in combination.
Other dibasic acids having 4 to 36 carbon atoms may be further used as a reactive monomer, examples include, but are not limited to, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid; terephthalic acid, isophthalic acid, phthalic anhydride; 1, 4-cyclohexanedicarboxylic acid, an octadecanunsaturated fatty acid dimer, maleic anhydride, and the like. In one embodiment of the invention, at least 30 mole% of 2-mSA, preferably at least 32 mole% of 2-mSA, more preferably at least 40 mole% of 2-mSA, based on the total moles of reactant monomers used, are used. In one embodiment of the invention, at least 60 mole%, at least 70 mole%, at least 80 mole%, or at least 90 mole% of 2-mSA, or only 2-mSA, based on the total moles of polyacid monomers used, is used as the reactive monomer for the polyacid. Anhydrides or esters of the foregoing acids may also be used as reactive monomers.
Characteristics of
The polyester polyol provided by the invention has high biomass content, and meets the requirement of the present day for continuous development. The biomass content is >30%, preferably >40%, more preferably >50%, for example, within a reasonable range consisting of the following endpoints: 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%. In one embodiment of the invention, the biomass content of the polyester polyol is 30% to 100%, preferably 50% to 100%, more preferably 80% to 100%. The related international detecting instrument for the content of the biomass material comprises a proportion counter, a liquid scintillation counter and an accelerator mass spectrometer, wherein a test target substance is a carbon 14 (14C) isotope in a sample, and the content of the biomass carbon source is calculated after the comparison with a standard value, namely the biomass content.
The high biomass content polyester polyols provided herein, which also meet the color specification required in the industry, in one aspect of the invention, exhibit an APHA color of no more than 30, preferably no more than 20, more preferably no more than 15.
In one embodiment of the invention, the high biomass polyester polyol has a weight average molecular weight in the range of 500 to 6,000, preferably 800 to 5500, more preferably 1000 to 4500, wherein for example: 600. 700, 800, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000, 3200, 3400, 3600, 3800, 4000, 4200, 4400, 4600, or 4800, preferably 1,000 to 4,000. Since polyester polyol can be used as a soft segment part in the synthesis of polyurethane, the invention provides high-biomass-content polyester polyol, if the molecular weight of the polyester polyol is too high, the polyester polyol has high proportion in polyurethane, and the degradation speed of the polyurethane can be too high, so that the polyester polyol cannot be easily applied to market products; too low a molecular weight of the polyester polyol, a low soft segment ratio, may result in a polyurethane that is too hard and inelastic. Therefore, in one embodiment, the synthetic formulation is adjusted so that the molecular weight of the prepared high biomass polyester polyol falls between 1000 and 4000, so that the product (high elasticity, high toughness and high reverse elasticity) meeting the market demand can be prepared more easily, and the physical property maintenance rate can reach more than three years.
In one particular aspect of the invention, the high biomass polyester polyol has an acid number in the range of <2mgKOH/g, preferably <1mgKOH/g, more preferably <0.5mgKOH/g. Too high an acid value is liable to hydrolyze, and for example, if the acid value is higher than 2mgKOH/g, hydrolysis resistance and reactivity are poor, and a hydrolysis resistance agent may be additionally added to improve hydrolysis resistance.
In one embodiment of the present invention, the hydroxyl number of the high biomass polyester polyol ranges from 15 to 220mgKOH/g, preferably from 20to 140mgKOH/g, more preferably from 28 to 100mgKOH/g.
Preparation method of high-biomass polyester polyol
As described above, the process for producing a polyester polyol of the present invention comprises reacting 2-methylsuccinic acid with a diol and optionally further added a dibasic acid.
In one embodiment of the invention, the process for preparing a high biomass polyester polyol comprises at least the steps of:
(1) Adding an alkyl polyol, an alkyl polyacid, and an antioxidant system to a reactor;
(2) The reaction is carried out under the stable gas environment at the temperature of not higher than 160 ℃, and then the reaction temperature is increased to 180-230 ℃ for continuous reaction;
(3) When the acid value is lower than the first target value, vacuum condition is applied to the reactor and the reaction is continued;
(4) The reaction is completed when the acid value is lower than the second target value;
wherein the alkyl polyacid comprises at least 2-methyl succinic acid and the antioxidant system comprises at least two antioxidants.
In one embodiment of the present invention, the stabilizing gas of step (2) comprises nitrogen, inert gas, and the like. In one embodiment of the present invention, the reaction of step (2) further comprises the use of a catalyst, examples including, but not limited to, one or more of tin catalysts (e.g., T-9 catalyst, T-12 catalyst), titanium catalysts (e.g., TBT), bismuth catalysts, zinc catalysts, and the like.
In one embodiment of the invention, the antioxidant system comprises a phosphite, a hindered amine complex antioxidant. Examples of phosphite antioxidants may be antioxidants 168, 618, 626. An example of a hindered amine complex antioxidant may be antioxidant 5057.
In one embodiment of the present invention, the reaction in step (2) is carried out at a temperature of not higher than 160 ℃, 130 to 150 ℃, preferably 135 to 145 ℃, more preferably 138 to 142 ℃ or about 140 ℃, or a reasonable range of temperatures consisting of the above numerical ranges for 0.5 to 5 hours, preferably 0.5 to 3 hours, more preferably 1 to 2 hours, if the reaction time is too short, the acid and alcohol reactions are incomplete, the monomer residues are more, the product chromaticity is poor due to poor heat resistance of the monomer, the reaction time is too long, the overall synthesis reaction time is prolonged, the catalyst efficiency is poor with the reaction time, and the acid value is difficult to decrease; the reaction temperature is then raised to 180 to 230℃and preferably at a temperature of 200 to 230 ℃. Without being limited by theory, it is known that 2-methylsuccinic acid, which contains pendant groups, may have a slower reaction rate and the monomer has poor heat resistance, reacts at a lower temperature; if the reaction is carried out directly at a temperature higher than 180 ℃, the problem of color depth tends to occur. In addition, the content of iron ions in 2-methyl succinic acid obtained from biomass sources is generally higher, so that the chromaticity of polyester polyol prepared from the polyester polyol is easily higher than that of the polyester polyol prepared from the polyester polyol by using the diacid from petrochemical sources.
In one embodiment of the present invention, wherein the 2-methyl succinic acid-containing bio-polyester polyol may prepare a polyester polyol having a weight average molecular weight of 500 to 6000.
In one embodiment of the invention, the first target value of step (3) is below 30mgKOH/g, preferably below 25mgKOH/g, more preferably below 20mgKOH/g. In one embodiment of the present invention, the second target value of step (4) is less than 1mgKOH/g, preferably less than 0.8mgKOH/g, more preferably less than 0.5mgKOH/g. In one embodiment of the present invention, the vacuum condition of step (3) may be <60torr (vacuum level > -700 torr)
Material
Antioxidant 168: CAS number 315710-04-4.
Antioxidant 5057: CAS number 68411-46-1.
Antioxidant 1010: CAS number 6683-19-8.
T-9 catalyst: CAS number 301-10-0, stannous isooctanoate.
T-12 catalyst: CAS number 77-58-7, dibutyl tin dilaurate.
TBT: CAS number 5593-70-4, tetra-n-butyl titanate.
Examples
Example 1
2-methylsuccinic acid (2-mSA): 400g, ethylene Glycol (EG): 100g, butylene Glycol (BG): 150g, antioxidant 168:0.06g, antioxidant 5057:0.02g, T-9 catalyst: 0.08g is added into a reaction vessel, nitrogen is introduced, the temperature is heated to 140 ℃ and stirred for 1hr, the mixture is heated to 180-230 ℃ for reaction, when the acid value is lower than 20mg KOH/g, vacuum is pumped to gradually increase the vacuum degree to-720 torr and the temperature is maintained for 7 hours, and the reaction is stopped when the acid value is lower than 1.
Example 2
2-methylsuccinic acid: 400g of ethylene glycol: 98g, butanediol: 140g, antioxidant 168:0.06g, antioxidant 5057:0.02g, T-9 catalyst: 0.08g is added into a reaction vessel, nitrogen is introduced, the mixture is heated to 140 ℃ and stirred for 1hr, then the mixture is heated to 180-230 ℃ for reaction, when the acid value is lower than 20mg KOH/g, vacuum is pumped to gradually increase the vacuum degree to-720 torr and the temperature is maintained for 7 hours, and the reaction is stopped when the acid value is lower than 1
Example 3
2-methylsuccinic acid: 400g, propylene Glycol (PG): 280g, antioxidant 168:0.06g, antioxidant 5057:0.02g, T-9 catalyst: 0.08g is added into a reaction vessel, nitrogen is introduced, the temperature is heated to 140 ℃ and stirred for 1hr, the mixture is heated to 180-230 ℃ for reaction, when the acid value is lower than 20mg KOH/g, vacuum is pumped to gradually increase the vacuum degree to-720 torr and the temperature is maintained for 7 hours, and the reaction is stopped when the acid value is lower than 1.
Example 4
2-methylsuccinic acid: 400g, propylene glycol: 250g, antioxidant 168:0.06g, antioxidant 5057:0.02g, T-9 catalyst: 0.08g is added into a reaction vessel, nitrogen is introduced, the temperature is heated to 140 ℃ and stirred for 1hr, the mixture is heated to 180-230 ℃ for reaction, when the acid value is lower than 20mg KOH/g, vacuum is pumped to gradually increase the vacuum degree to-720 torr and the temperature is maintained for 7 hours, and the reaction is stopped when the acid value is lower than 1.
Example 5
2-methylsuccinic acid: 400g, propylene glycol: 242g, antioxidant 168:0.06g, antioxidant 5057:0.02g, T-9 catalyst: 0.08g is added into a reaction vessel, nitrogen is introduced, the temperature is heated to 140 ℃ and stirred for 1hr, the mixture is heated to 180-230 ℃ for reaction, when the acid value is lower than 20mg KOH/g, vacuum is pumped to gradually increase the vacuum degree to-720 torr and the temperature is maintained for 7 hours, and the reaction is stopped when the acid value is lower than 1.
Example 6
2-methylsuccinic acid: 400g, propylene glycol: 242g, antioxidant 168:0.06g, antioxidant 5057:0.02g, TBT catalyst: 0.08g is added into a reaction vessel, nitrogen is introduced, the temperature is heated to 140 ℃ and stirred for 1hr, the mixture is heated to 180-230 ℃ for reaction, when the acid value is lower than 20mg KOH/g, vacuum is pumped to gradually increase the vacuum degree to-720 torr and the temperature is maintained for 7 hours, and the reaction is stopped when the acid value is lower than 1.
Comparative example 1
2-methylsuccinic acid: 400g of ethylene glycol: 100g, butanediol: 150g, antioxidant 1010:0.1g, TBT:0.08g is added into a reaction vessel, nitrogen is introduced, the temperature is heated to 180-230 ℃ and stirred, when the acid value is lower than 20mg KOH/g, vacuum is pumped to gradually increase the vacuum degree to-720 torr and the temperature is maintained for 7 hours, and the reaction is stopped when the acid value is lower than 1.
Comparative example 2
2-methylsuccinic acid: 400g, propylene glycol: 250g, antioxidant 1010:0.1g, TBT:0.08g is added into a reaction vessel, nitrogen is introduced, the temperature is heated to 180-230 ℃ and stirred, when the acid value is lower than 20mg KOH/g, vacuum is pumped to gradually increase the vacuum degree to-720 torr and the temperature is maintained for 7 hours, and the reaction is stopped when the acid value is lower than 1.
Comparative example 3
2-methylsuccinic acid: 400g of ethylene glycol: 100g, butanediol: 150g, antioxidant 168:0.06g, antioxidant 5057:0.02g, T-9 catalyst: 0.08g is added into a reaction vessel, nitrogen is introduced, the temperature is heated to 180-230 ℃ and stirred, when the acid value is lower than 20mg KOH/g, vacuum is pumped to gradually increase the vacuum degree to-720 torr and the temperature is maintained for 7 hours, and the reaction is stopped when the acid value is lower than 1.
Efficacy assessment
The following methods were used to evaluate the properties of the polyester polyols of the examples.
Acid value: according to ASTM D4662
Hydroxyl value: according to ASTM D6342
APHA color: according to ASTM D4890
The polyester polyols provided by the present invention, while achieving the goal of high biomass content, also exhibit excellent APHA color values.

Claims (2)

1. A process for preparing a high biomass polyester polyol comprising the steps of:
400g of 2-methyl succinic acid, 100g of ethylene glycol, 150g of butanediol, and 168 of antioxidant: 0.06g, antioxidant 5057:0.02g, T-9 catalyst: adding 0.08g into a reaction vessel, introducing nitrogen, heating to 140 ℃ and stirring for 1hr, heating to 180-230 ℃ and reacting, when the acid value is lower than 20mg KOH/g, vacuumizing to gradually increase the vacuum degree to-720 torr and maintaining the temperature for 7 hours, and stopping the reaction when the acid value is lower than 1.
2. A high biomass polyester polyol prepared by the process of claim 1.
CN201911292836.2A 2019-12-16 2019-12-16 Preparation of high biomass polyester polyols from hydrogenated itaconic acid Active CN112979930B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08301968A (en) * 1995-04-28 1996-11-19 Kuraray Co Ltd Production of polyurethane
CN105218792A (en) * 2015-10-16 2016-01-06 广东大盈化工有限公司 Environment-friendly type polyester polyvalent alcohol and preparation method thereof
CN105399937A (en) * 2015-12-16 2016-03-16 南京工业大学 Preparation method of polyester polyol

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08301968A (en) * 1995-04-28 1996-11-19 Kuraray Co Ltd Production of polyurethane
CN105218792A (en) * 2015-10-16 2016-01-06 广东大盈化工有限公司 Environment-friendly type polyester polyvalent alcohol and preparation method thereof
CN105399937A (en) * 2015-12-16 2016-03-16 南京工业大学 Preparation method of polyester polyol

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