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CN118496489A - Method for preparing polyether ester polyol and product thereof - Google Patents

Method for preparing polyether ester polyol and product thereof Download PDF

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Publication number
CN118496489A
CN118496489A CN202310424908.4A CN202310424908A CN118496489A CN 118496489 A CN118496489 A CN 118496489A CN 202310424908 A CN202310424908 A CN 202310424908A CN 118496489 A CN118496489 A CN 118496489A
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China
Prior art keywords
polyol
polyether
polyester
glycol
polyether ester
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Pending
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CN202310424908.4A
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Chinese (zh)
Inventor
乔建强
李锐
崔跃伟
田松
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ZHENGZHOU ZHONGYUAN SPANDEX ENGINEERING TECHNOLOGY CO LTD
Original Assignee
ZHENGZHOU ZHONGYUAN SPANDEX ENGINEERING TECHNOLOGY CO LTD
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Priority to CN202310424908.4A priority Critical patent/CN118496489A/en
Priority to PCT/CN2024/088284 priority patent/WO2024217450A1/en
Publication of CN118496489A publication Critical patent/CN118496489A/en
Pending legal-status Critical Current

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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
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—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
    • 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
    • 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
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • 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
    • C08G18/48—Polyethers
    • 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
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products

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

Abstract

The invention provides a method for preparing polyether ester polyol and a product thereof, wherein polyether glycol and polyester are used as raw materials to be added into a reaction kettle, the reaction kettle is heated to the reaction temperature for transesterification, and micromolecular polyol produced by the transesterification is distilled out by adopting a vacuum distillation method, so that the polyether ester polyol is prepared. Wherein the polyester contains an aromatic diacid polyol ester structure, the polymerization degree of polyether glycol is 2-20, the molecular weight is 100-1000, the molar ratio of the aromatic group structure in the polyether glycol and the polyester is more than 1.05:1, the reaction temperature is above the boiling point of the micromolecular polyol, and the boiling point of the polyether glycol is below. The method provided by the invention can directly process the recycled polyester into the polyether ester polyol suitable for producing polyurethane elastic fibers, simplifies the production flow of the polyether ester polyol suitable for producing spandex, and widens the raw material sources of the polyurethane elastic fibers while utilizing the recycled resources.

Description

Method for preparing polyether ester polyol and product thereof
Technical Field
The invention relates to the field of preparation methods of polymers, in particular to a method for preparing polyether ester polyol and a product thereof.
Background
The polyester is an engineering material with excellent performance and wide application, particularly the polyester with benzene rings in structures such as polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT) and the like is particularly common, and can be used as fiber, bottle, film or other plastic products, and is an indispensable plastic variety in daily life of people. With the increasing use of polyester plastic products, environmental problems caused by non-degradable polyester plastics are increasingly received attention by people. Plastic recycling is an effective means for solving the environmental problem, and the main polyester plastic recycling method at present is to re-melt and granulate plastic bottle flakes as recycling materials, and re-process the plastic bottle flakes to prepare plastic products. However, the method has higher requirements on the quality of the recycled plastic bottle flakes, less impurities, small color difference and small molecular weight difference, and many plastic wastes which do not reach the above standards are difficult to recycle. In addition to recycling and granulating, there are methods of decomposing recycled polyester plastics into terephthalic acid (PTA) or dimethyl terephthalate (DMT) by a chemical method after removing impurities and reusing the terephthalic acid or dimethyl terephthalate (DMT) as a chemical raw material, but the method is complex in process, the purity of the prepared product is difficult to ensure, and the recycling of the prepared product is limited in application.
Spandex is an abbreviation of polyurethane elastic fiber, is the most widely used elastic fiber at present, and is a segmented copolymer of soft segments and hard segments, wherein the soft segments are generally composed of soft segments, and the soft segments are generally obtained by reacting polyols such as polyether, polyester, hydroxyl-terminated polybutadiene and the like with polyisocyanates for connecting the polyols; the hard segment is composed of segments with excellent crystallization performance, and is generally obtained by reacting polyisocyanate with small molecular polyol and small molecular amine chain extender. The main raw materials of the dry-method polyether type spandex are polytetrahydrofuran ether glycol, diphenylmethane diisocyanate and chain-extended amines, a polyurethane urea solution is prepared through a two-step polymerization reaction, then necessary additives are added to prepare a polyurethane urea spinning solution, and the polyurethane urea spinning solution is prepared through channel spinning. The method adopts polytetrahydrofuran ether glycol as a soft chain segment, the prepared spandex fiber has balanced performance, generally has higher elastic elongation, and the tensile modulus of the spandex fiber can basically meet the daily clothing requirement. But at a higher cost and this method does not allow the use of recycled materials.
The inventor finds in long-term research that the polyether ester polyol with aromatic group-polyether block is used as a soft chain segment of spandex, and can also prepare the spandex with high elongation and high elastic recovery rate. The elastic modulus and elastic recovery rate of the spandex can be adjusted by adding a small amount of small molecular diol structure into the block structure of the polyether ester polyol. And the polyether ester polyol has a structure similar to that of common polyester, and provides possibility for recycling polyester as a spandex raw material. In general, the polyether ester polyol is prepared by reacting dicarboxylic acid having aromatic groups with polyether glycol, and the process for preparing terephthalic acid by recovering polyester is complicated, energy consumption is high, and purification difficulty is high, so the present invention has been made in an effort to provide a method for preparing polyether ester polyol suitable for producing spandex by recovering polyester, in order to simplify the production flow of polyether ester polyol.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for preparing a polyetherester polyol suitable for producing spandex from polyester as a raw material, the polyetherester polyol prepared by the method, and polyurethane elastic fibers, non-woven fabrics, films and elastomers prepared by using the polyetherester polyol, and methods thereof. The specific scheme is as follows:
A process for preparing a polyetherester polyol comprising the steps of:
Step 1) adding polyether glycol and polyester as raw materials into a reaction kettle, wherein the polyester contains an aromatic dibasic acid polyol ester structure, the polymerization degree of the polyether glycol is 2-20, the molecular weight is 100-1000, and the molar ratio of aromatic groups in the polyether glycol and the polyester is more than 1.05:1;
and 2) heating the reaction kettle to a reaction temperature to perform transesterification, and evaporating micromolecular polyol produced by the transesterification by adopting a vacuum distillation method to prepare the polyether ester polyol, wherein the reaction temperature is higher than the boiling point of the micromolecular polyol and lower than the boiling point of the polyether glycol.
In the above method, the aromatic dibasic acid polyol ester structure refers to an ester structure formed by an aromatic dibasic acid and a polyol in the polyester. Wherein the aromatic includes an aromatic ring structure and an aromatic heterocyclic structure, wherein the aromatic ring may be at least one of an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like; the aromatic heterocycle may be at least one of pyridine, furan ring, thiazole ring, pyrimidine ring, etc., and specifically, the aromatic dibasic acid may be one or more of terephthalic acid, phthalic acid, isophthalic acid, biphenyl dicarboxylic acid, 1, 4-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, 2, 3-naphthalene dicarboxylic acid, 2, 5-furan dicarboxylic acid, terephthallic acid, isophthalic acid, phthalic acid. The polyalcohol is one or more of dihydric alcohol, trihydric alcohol and tetrahydric alcohol, preferably dihydric alcohol, more preferably one or more of ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, 2-methyl-1, 3-propylene glycol and 3-methyl-1, 5-pentanediol.
Alternatively, the polyester containing the aromatic dibasic acid polyol ester structure in the present invention may be one or more of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polybutylene terephthalate (PTT), polybutylene adipate and polybutylene terephthalate copolymer (PBAT), and polyethylene 2, 5-furandicarboxylate (PEF). The polyester containing an aromatic diacid polyol ester structure may also be any other common polyester containing a polyetherester structure or a triol, tetraol residue structure, provided that the aromatic diacid polyol ester structure is contained in its backbone as a starting material in the process of the present invention.
Optionally, the polyether glycol is a homo-or co-polyether glycol prepared by condensation polymerization of small molecular glycols of C2-C5 or ring-opening polymerization of epoxides of C2-C5, and specifically, one or more of polyethylene glycol (PEG), poly-1, 3-propanediol (P3 OG), poly-1, 2-propanediol (PPG), polytetrahydrofuran (PTG), polyethylene glycol-1, 2-propanediol copolymer and polytetrahydrofuran-3-methyltetrahydrofuran copolymer are preferred.
Alternatively, the molar ratio of aromatic group structure in the polyether diol and the polyester is calculated by the following formula:
R＝(W+P-36)/(W-A)
In the method, in the process of the invention,
R is the mole ratio of polyether glycol to aromatic group structure in polyester,
W is the molecular weight of the target polyether ester polyol, and W is 1000-5000,
P is the molecular weight of aromatic diacid in the polyester feedstock,
A is the average molecular weight of the polyether glycol.
Wherein the aromatic dibasic acid in the raw material of the polyester is a dibasic acid raw material forming the aromatic dibasic acid polyol ester structure, such as terephthalic acid, phthalic acid, 2, 5-furandicarboxylic acid and the like as described above.
Polyetherester polyol obtainable by the process for preparing polyetherester polyol as described hereinbefore, characterized in that the polyetherester polyol comprises a structure and capped alcoholic hydroxyl groups as shown in the following formula (1) and the following formula (2):
Wherein R 1 is an aromatic group, the mass content of R 1 in the repeating unit of the formula (1) is 4.5-44%, R 2 is at least one of saturated alkane groups with 2-5 carbon atoms, x is 2-20, and R 3 is the residue of polyhydric alcohol in the polyester raw material;
The mass ratio of formula (2) in the structure of the polyetherester polyol is less than 20%, preferably less than 10%;
The polyether ester polyol has a number average molecular weight of 1000-5000;
the average functionality of the blocked alcoholic hydroxyl groups is 1.95-2.00.
Preferably, R 2 is at least two of saturated alkyl groups with 2-5 carbon atoms.
The polyether ester polyol can be used for preparing spandex and other polyurethane products. The present invention therefore also provides a process for preparing polyurethane elastic fibers, nonwovens, films or elastomers in solution processing or melt processing using the abovementioned polyetherester polyols as starting materials. And polyurethane elastic fiber, nonwoven, film or elastomer produced according to the method.
The beneficial effects are that:
The method for preparing polyether ester polyol provided by the invention adopts polyester as a raw material, can directly process the recycled polyester into polyether ester polyol suitable for producing spandex, simplifies the production flow of polyether ester polyol suitable for producing spandex, utilizes the recycled resource, and widens the raw material source of polyurethane elastic fiber.
Detailed Description
For recycling of polyester materials, the most common mode at present is to use melt-pelletization recycling, or chemical decomposition into terephthalic acid (PTA) or dimethyl terephthalate (DMT) as chemical raw materials for recycling. The invention discovers a method for preparing polyether ester polyol, which uses polyester as a raw material, wherein the prepared polyether ester polyol can be used as a soft segment raw material of spandex, and the method can be used for directly taking polyester as a raw material of polyurethane elastic fiber, so that the application of the recycled polyester is widened, and the raw material source of the spandex is also expanded.
Specifically, the invention provides a method for preparing polyether ester polyol, and polyether ester polyol prepared by the method, wherein the polyether ester polyol comprises a structure and end capping alcohol hydroxyl groups shown in the following formula (1) and the following formula (2):
Wherein R 1 is an aromatic group structure, the mass content of R 1 in the repeating unit of the formula (1) is 4.5-44%, R 2 is at least one of saturated alkane groups with 2-5 carbon atoms, x is 2-20, and R 3 is the residue of polyhydric alcohol in the polyester raw material;
The mass ratio of formula (2) in the structure of the polyetherester polyol is less than 20%, preferably less than 10%, more preferably 0;
The polyether ester polyol has a number average molecular weight of 1000-5000;
The average functionality of the hydroxyl groups of the capped alcohol is from 1.95 to 2.00.
Hereinafter, unless otherwise specified, the polyether ester polyol refers to a polyether ester polyol having the above-mentioned characteristics.
The aromatic group structure comprises an aromatic ring and an aromatic heterocyclic ring, wherein the aromatic ring can be at least one of aromatic rings such as benzene ring, naphthalene ring, anthracene ring, phenanthrene ring and the like; the aromatic heterocycle may be at least one of pyridine, furan ring, thiazole ring, pyrimidine ring, and the like. When the content of the aromatic group R 1 in the polyether ester polyol is too high, the final polyether ester polyol is excessively rigid, and thus excessively high in viscosity, which is disadvantageous in the polyurethane elastic fiber production process, so that the mass content of R 1 in the repeating unit of formula (1) is 4.5% -44%.
The structure of the formula (2) is a residual structure of the polyester which is not completely reacted in the method of the present invention, and since the reaction of the present invention is generally not hundred percent complete, a part of the group structure of the polyester raw material remains, and therefore, a part of the structural unit of the formula (2) may exist in the finally produced polyether ester polyol, but the transesterification reaction can be made as complete as possible by controlling the reaction conditions. The structure of formula (2) can obviously increase the melting point of polyether ester polyol, can also increase the intermolecular acting force of polyether ester diol, and can cause excessive prepolymer viscosity during prepolymerization to be incapable of completing the prepolymerization reaction. And the aromatic dibasic acid polyol ester structure also affects the elastic recovery of the final polyurethane, resulting in lower elastic recovery and greater permanent set, the mass ratio of formula (2) in the polyether ester polyol structure of the present invention is less than 20%, preferably less than 10%, more preferably 0.
According to the invention, the average functionality of the blocked polyol hydroxyl groups of the polyetherester polyol may be from 1.95 to 2.00, preferably from 1.96 to 2.00, more preferably from 1.98 to 2.00, which ensures that the polyetherester polyol is successfully isocyanate blocked and subsequently chain extended by small molecule amines or alcohols. If the average functionality is more than 2.00, when the polyether ester polyol is used as a raw material for preparing polyurethane, it may cause the prepared polyurethane to have a crosslinked structure, thereby failing to form polyurethane in a chain shape; the polyurethane can generate gel in continuous production, which prevents continuous production of spandex. If the average functionality is small, the molecular weight of the polyurethane produced will also be low, thereby affecting the properties of the polyurethane elastic fiber. In the actual reaction, the hydroxyl end groups of the polyether glycol are possibly dehydrated to form double bonds in the condensation polymerization/ring-opening polymerization process, and the polycondensation reaction or the transesterification reaction of the polyether glycol to form the polyether ester polyol cannot be completed by 100% due to the limitation of the actual reaction effect, so that the average functionality of the final polyether ester polyol cannot generally reach 2.00.
Herein, "average functionality" means the average number of moles of alcoholic hydroxyl groups per mole of polyetherester polyol that can participate in the reaction, and in the present invention, the average functionality of alcoholic hydroxyl groups can be calculated by the following formula, taking into account the dehydration of the terminal hydroxyl groups of the polyether diol to form double bonds, and the presence of unreacted carboxyl groups:
functionality = 2 moles of alcoholic hydroxyl groups/(moles of alcoholic hydroxyl groups + moles of carboxyl groups + moles of double bonds)
The polyether ester polyol of the present invention may have a melting point below 80 c, preferably in a liquid state at normal temperature, so that it is prevented from solidifying during storage or transportation to ensure industrial continuous operation. Otherwise, the alloy needs to be melted by heating, so that the energy consumption is increased.
The inventor finds that the polyether ester polyol with the characteristics can replace polytetrahydrofuran ether glycol to be used as a soft segment raw material of spandex, and the prepared spandex has higher elastic recovery rate. On the basis, the inventor provides a method for preparing the polyether ester polyol, compared with the conventional mode of adopting dicarboxylic acid to react with polyether glycol, the method for preparing the polyether ester polyol by using recycled polyester as a raw material widens the utilization mode of the recycled polyester, widens the source of spandex raw material, and simultaneously accords with the environmental protection concept.
The specific preparation method of the polyether ester polyol provided by the invention comprises the following steps:
Step 1) adding polyether glycol and polyester as raw materials into a reaction kettle, wherein the polyester contains an aromatic dibasic acid polyol ester structure, the polymerization degree of the polyether glycol is 2-20, preferably 3-10, the molecular weight is 100-1000, and the molar ratio of aromatic groups in the polyether glycol and the polyester is more than 1.05:1;
and 2) heating the reaction kettle to a reaction temperature to perform transesterification, and evaporating micromolecular polyol produced by the transesterification by adopting a vacuum distillation method to prepare the polyether ester polyol, wherein the reaction temperature is higher than the boiling point of the micromolecular polyol and lower than the boiling point of the polyether glycol.
In the method of the invention, polyester containing aromatic group structure and specific polyether glycol are used as raw materials to carry out transesterification reaction, so as to prepare polyether ester polyol meeting the characteristics. The polyether ester polyol molecular structure prepared by the invention is an aromatic group-polyether structure connected by ester bonds, so the method selects polyester containing the aromatic group structure as a raw material, and the aromatic group structure in the polyester is introduced into the molecular structure of the polyether ester polyol. Specifically, the polyester containing an aromatic group structure may be any common polyester material formed by copolymerizing an aromatic group and a small-molecule polyol, such as polyethylene terephthalate (PET), polypropylene terephthalate (PTT), polybutylene terephthalate (PBT), polybutylene adipate and polybutylene terephthalate copolymer (PBAT) containing aromatic acid esters in the structure; or polyesters containing aromatic hetero acid esters in the structure such as polyethylene 2, 5-furandicarboxylate (PEF) and the like, which are all obtainable by recycling polyester plastic bottles, polyester fibers, polyester films and the like. Compared with a rigid aromatic group structure, the polyether chain segment in the polyether ester polyol provides elasticity for molecules, so that the finally prepared spandex has enough elastic recovery capacity, the polyether chain segment has a certain length, if the length of the polyether chain segment is too short, the viscosity of the polyether ester polyol is too high, the continuous mass production process of the spandex is not facilitated, and the elastic recovery performance of the spandex is poor; the polyether chain segment length is too long, which can cause too poor elastic modulus of spandex, so that the molecular weight of the preferable polyether chain segment raw material is polyether glycol with the preferable polymerization degree of 2-20, more preferably 3-10 and the molecular weight of 100-1000, preferably 300-1000, more preferably 600-900, and specifically, the polyether glycol can be synthesized by ring-opening polymerization of epoxy monomers or polycondensation of small molecular glycol; either as a homopolymer synthesized from a single monomer or as a copolymer synthesized from two or more monomers. By way of example, polyether diols suitable for use in the present invention may be one or more of diethylene glycol (DEG), triethylene glycol (TEG) polyethylene glycol (PEG), poly-1, 3-propanediol (P3 OG), polypropylene glycol (PPG), polytetrahydrofuran (PTG), or copolymer diols obtained by reacting tetrahydrofuran with monomers such as ethylene oxide, propylene oxide, 2-methyltetrahydrofuran, or 3-methyltetrahydrofuran.
The polyetherester polyols of the present invention should have a number average molecular weight of from 1000 to 5000, preferably from 1000 to 3500, more preferably from 1400 to 2500, most preferably from 1500 to 2300. The higher the number average molecular weight of the polyether ester polyol, the higher the viscosity thereof, and it is difficult to conduct continuous operation on an industrial scale. However, when the molecular weight of the polyether ester polyol is too small, more diisocyanate is required to participate in synthesis when the molecular weight of the polyurethane prepolymer is required to be consistent, so that the content of urethane groups in the prepolymer is higher, the interaction between prepolymer molecules is enhanced, and the viscosity is increased. Moreover, the short length of the soft segments in the polyurethane formed at this time affects the recovery properties of the final polyurethane elastic fiber. In a preferred embodiment, the polyetherester polyols of the present invention may have a viscosity of less than 500 poise, preferably less than 200 poise, at 90℃and a shear rate of 1S -1.
Since the method provided by the invention is to prepare polyether ester polyol by adopting polyether glycol to carry out transesterification reaction on polyester containing aromatic groups, the molecular weight of the polyether ester polyol can be adjusted by adjusting the molar ratio R of the aromatic groups in the polyether glycol and the polyester, and the molar ratio R refers to the molar ratio of the aromatic groups in the polyether glycol and the polyester. The higher the above molar ratio R, i.e. the more the ratio of polyether glycol in the raw material, the more the hydroxyl end groups left after the small molecular polyol residues in the polyester polymer compound are replaced by the polyether glycol, the smaller the number average molecular weight of the prepared polyether ester polyol; conversely, the smaller the ratio of polyether glycol in the raw material, the greater the number average molecular weight of the polyether ester polyol produced. In order to play a role in regulating the molecular weight of the polyether ester polyol, the mole number of the polyether glycol is larger than that of an aromatic group structure in the polyester, in theory, when the transesterification reaction is complete, the polyether glycol replaces all small molecular polyol residues in the polyester, and the excessive polyether glycol cuts the polyester molecular chain of a macromolecule to form the polyether ester polyol with relatively smaller molecular weight, so that the difference between the mole number of the polyether glycol and the mole number of the aromatic group structure in the polyester is the mole number of the finally obtained polyether ester polyol. From the above analysis, the calculation method of the theoretical expected molecular weight of the finally prepared polyetherester polyol is:
The molar ratio R of aromatic groups in specific polyether glycol and polyester can be obtained by reverse-pushing the formula, and the specific process is as follows:
Setting the molecular weight of the finally obtained polyether ester polyol as W, setting the molecular weight of the polyether glycol as A, and setting the feeding mole number as M, wherein the feeding quality of the polyether glycol is M.A; the polyester is obtained by reacting aromatic dibasic acid with molecular weight P and micromolecular polyol with molecular weight Q, the molecular weight of a polyester circulation unit is (P+Q-36), the mole number of an aromatic group structure in the fed polyester is M/R, and the fed mass of the polyester is (P+Q-36). M/R; substituting the above letters into formula (1) yields the following formula:
the formula (4) is simplified to obtain the relational expression between the molecular weight W of the polyether ester polyol and the feeding molar ratio R as follows:
When polyether ester polyol with specific molecular weight is required to be prepared through the formula (5), the feeding molar ratio R can be calculated by the following formula:
as is clear from the formula (6), in order to obtain a polyether ester polyol having a molecular weight W of 1000 to 5000, the molar ratio R is related to the molecular weight P of the aromatic dibasic acid and the molecular weight A of the polyether diol. However, it is determined that the number of moles of polyether diol in step (1) should be greater than the number of moles of aromatic groups in the polyester, and therefore the molar ratio of polyether diol to aromatic groups in the polyester in the present invention is greater than 1.05:1, preferably greater than 1.1:1.
In the step (2), the temperature of the transesterification reaction should be controlled to be higher than the boiling point of the small molecular polyol and lower than the boiling point of the polyether glycol, so that the exchanged small molecular polyol can be distilled out as much as possible, and the transesterification is promoted to be completely carried out.
In the transesterification reaction, a catalyst is preferably added to promote the reaction, and in the present invention, the catalyst is selected from one or more of titanium, vanadium, tin, antimony, zirconium, bismuth and rare earth catalysts, preferably one or more of tetraisopropyl titanate, tetrabutyl titanate, dibutyl tin dilaurate, stannous octoate and bismuth laurate.
The invention also provides a method for preparing polyurethane products such as polyurethane elastic fiber, non-woven fabrics, films or elastomers by taking the polyether ester polyol or the polyether ester polyol prepared by the method as a raw material. The preparation method of the polyurethane can adopt a two-step method for synthesizing the prepolymer, and can also adopt a one-pot method for feeding together.
Wherein, the two-step method for preparing polyurethane comprises the following steps: (1) Reacting a polyetherester polyol with a diisocyanate to form a prepolymer; and (2) polymerizing the prepolymer with a chain extender and a chain terminator. The method for preparing polyurethane by the one-pot method comprises the following steps: (1) Feeding polyether ester polyol, diisocyanate and micromolecular polyol chain extender respectively, namely adding the materials into a reaction container respectively; (2) Polyether ester polyol, diisocyanate and micromolecular polyol chain extender are mixed in a reaction vessel, and the mixture is heated for reaction or heated for reaction in the mixing process. Wherein the diisocyanate may be selected from one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isomers thereof. The chain extender can be amine or alcohol chain extender, wherein the amine chain extender can be diamine with 2-30 carbon atoms, for example, one or more selected from ethylenediamine, propylenediamine, pentylene diamine, methylpentylenediamine, methylpropylenediamine, hexamethylenediamine, triethylenediamine, xylylenediamine, phenylenediamine, diaminocyclohexane, hexamethylenediamine and dopamine; the alcohol chain extender can be one or more of common chain extenders such as ethylene glycol, 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol, 1, 3-propanediol, 1, 4-dimethylolcyclohexane and the like. The chain terminator may be a monoamine having 2 to 20 carbon atoms and may be one or more selected from ethylamine, isopropylamine, n-butylamine, t-butylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, di-n-butylamine, di-t-butylamine, diisobutylamine, diisopropylamine, cyclohexylamine or ethanolamine.
The corresponding operating conditions, such as solution processing or melt processing, of the prior art methods for preparing polyurethane articles such as polyurethane elastic fibers, nonwoven fabrics, films and elastomers using polyether diols are applicable to the present invention, unless otherwise indicated herein. For example, polyurethane elastic fibers may be dry-spun using a polyurethane solution, such as the method and apparatus described in patent document CN1147628C, or melt-spun using a polyurethane chip, such as the melt-spinning method described in patent document CN 1180137C; the nonwoven fabric may be processed by melt-blowing, solution electrospinning, or the like, particularly by a melt-blown nonwoven fabric manufacturing method described in patent document CN101400838a, and a nonwoven fabric prepared by a solution electrospinning method described in patent document JP2009108422 a; the polyurethane film can be processed in the modes of solution blade coating, dip coating, melt extrusion, film blowing, casting and the like, and particularly, the polyurethane film is prepared in the blade coating mode described in patent document JP2005205787A, the dip coating mode described in patent document WO2015064776A1, the extrusion mode described in patent document GB1137520A, the film blowing mode described in patent document DE2239478A1 and the casting mode described in patent document JP 2004203933A; the elastomer may be processed by extrusion, injection molding, casting, etc., specifically by extrusion as described in JP1996027376A, injection molding as described in US3917792A, casting as described in CA1251294A, to prepare the polyurethane elastomer. The production methods of polyurethane articles described in the above patent documents are all incorporated into the present invention. The above-described methods of preparing polyurethane elastic fibers, nonwoven fabrics, films and elastomers are merely examples, and the polyetherester polyols of the present invention may be used as diol starting materials to produce polyurethane articles by any known techniques or means other than those mentioned above.
Examples
The invention is illustrated in more detail below by means of examples, in which the test methods for the parameters involved are as follows:
1. Average functionality:
Functionality = 2 moles of alcoholic hydroxyl groups/(moles of alcoholic hydroxyl groups + moles of carboxyl groups + moles of double bonds).
Wherein the acid value is measured by the method described in HG/T2708-1995; the hydroxyl number was measured as described in HG/T2709/1995; unsaturation was measured as described in GB/T12008.6-2010. The corresponding acid number, hydroxyl number, unsaturation are converted to the moles of the corresponding end groups in the polyetherester diol.
2. Tensile 300% stress, breaking strength and elongation at break: the method for testing the tensile property of the spandex filaments is all according to FZ/T50006-2013 of textile industry Standard of the people's republic of China.
3. Plastic deformation experiment:
and clamping one end of the prepared sample into the upper clamp holder, applying pre-tension to the other end of the prepared sample, enabling the sample to axially straighten and clamp into the lower clamp holder, and starting the instrument.
The specimen was stretched from 0% elongation L0 to 300% elongation L1 at a speed of 500mm/min, and then returned to 0% elongation, and the stretching was repeated four times; recording a force value F1 of 200% in the fifth stretching to 300% elongation, delaying for 30s, and recovering to 0% elongation, wherein in the fifth stretching, a force value F2 of 200% is recorded; after a delay of 30s, a sixth stretching is performed and the length L2 of the sample stretched to the pre-tension is recorded.
The calculation formula of the plastic deformation rate is as follows: (L2-L0)/L0 x 100%
Wherein "5LP200%" represents the stress value at 5 th stretch to 200% elongation, i.e., F1; "5UP200%" means the rebound stress value from tensile to 300% elongation to 200% elongation at 5 th time, F2, can be used to characterize the recovery modulus; "plastic deformation ratio" means the ratio of increase in the length of spandex filament compared to the original length after 5 stretches; "5UP200%/5LP 200%" means the ratio of 200% recovery stress to 200% tensile stress at 5 th tensile test for 5 tensile cycles.
In addition, the antioxidants mentioned in the examples below are antioxidants 245, dyeing assistants DH300R or 2462B, light stabilizers Tinuvin 791, which are commercially available.
In the examples below, the ratio of alkyd actually participating in the reaction is less than the theoretical value due to the effect of evaporating small molecular weight polyol as noncondensable gas and volatilization of small molecular weight components in polyether glycol during the reaction, and thus the molecular weight of the final product is larger than the theoretical value, but the deviation value is within an acceptable range.
Examples 1-6 below relate to the use of polyethylene terephthalate (PET) as a starting material for the preparation of polyetherester polyols.
Example 1 preparation of polyetherester polyol having molecular weight 1200
Firstly, crushing polyethylene terephthalate, adding 2081.9g of crushed polyethylene terephthalate (PET) and 3000g of polyethylene glycol (PEG 200) with the number average molecular weight of 200 into a reaction kettle (namely, the molar ratio is about 1.38), adding 3g of zinc acetate and 1.5g of Sb2O3 as catalysts, gradually heating to 235 ℃, starting the transesterification reaction, maintaining the temperature at 235 ℃ until the reaction system is homogeneous, and evaporating the glycol in the reaction system by adopting a vacuum distillation method until the evaporation amount of the glycol is close to a theoretical value, and evaporating 650g of the glycol from the reaction system. A polyetherester polyol having a molecular weight of 1200 was obtained. The polyether ester polyol has a viscosity of 1S -1 at 40 ℃ of 100Poise, an acid value of 0.3 and a pale yellow liquid at normal temperature.
Example 2 preparation of polyetherester polyol having a molecular weight of 2100
Firstly, crushing polyethylene terephthalate, adding 2428.9g of crushed polyethylene terephthalate (PET) and 3000g of polyethylene glycol (PEG 200) with the number average molecular weight of 200 into a reaction kettle (namely, the molar ratio is about 1.19), adding 3g of magnesium acetate and 1.5g of Sb2O3 as catalysts, gradually heating to 235 ℃, starting the transesterification reaction, maintaining the temperature at 235 ℃ until the reaction system is homogeneous, and evaporating the glycol in the reaction system by adopting a vacuum distillation method until the evaporation amount of the glycol is close to a theoretical value, and evaporating 781.9g of the glycol from the reaction system. A polyetherester polyol having a molecular weight of 2100 was obtained. The polyether ester polyol has a viscosity of 1S -1 at 40 ℃ of 210Poise, an acid value of 0.3 and a pale yellow liquid at normal temperature.
Example 3 preparation of polyetherester polyol having molecular weight 3400
Firstly, crushing polyethylene terephthalate, adding 2602.4g of crushed polyethylene terephthalate (PET) and 3000g of polyethylene glycol (PEG 200) with the number average molecular weight of 200 into a reaction kettle (namely, the molar ratio is about 1.11), adding 3g of zinc acetate and 1.5g of Sb2O3 as catalysts, gradually heating to 235 ℃, starting the transesterification reaction, maintaining the temperature at 235 ℃ until the reaction system is homogeneous, and evaporating the glycol in the reaction system by adopting a vacuum distillation method until the evaporation amount of the glycol is close to a theoretical value, and evaporating 842.3g of the glycol from the reaction system. A polyetherester polyol having a molecular weight of 3400 was obtained. The polyether ester polyol has a viscosity of 650Poise, an acid value of 0.3 and a pale yellow liquid at normal temperature of 1S -1 at 40 ℃.
Example 4 preparation of polyetherester polyol having molecular weight 1500
Firstly, crushing polyethylene terephthalate, taking 1296.5g of crushed polyethylene terephthalate (PET) and 4203g of polyethylene glycol (PEG 400) with the number average molecular weight of 400, adding into a reaction kettle (namely, the molar ratio is about 1.57), adding 3g of zinc acetate and 1.5g of Sb2O3 as catalysts, gradually heating to 245 ℃, starting transesterification, keeping 245 ℃ until the reaction system is homogeneous, and evaporating the glycol in the reaction system by adopting a vacuum distillation method until the evaporation amount of the glycol is close to a theoretical value, and evaporating 418.6g of the glycol from the reaction system. A polyetherester polyol having a molecular weight of 1500 was obtained. The polyether ester polyol has a viscosity of 1S -1 at 40 ℃ of 73.5Poise, an acid value of 0.3 and a pale yellow liquid at normal temperature.
Example 5 preparation of polyetherester polyol having a molecular weight of 3450
Firstly, crushing polyethylene terephthalate, taking 1019.2g of crushed polyethylene terephthalate (PET) and 4480g of polyethylene glycol (PTG 650) with the number average molecular weight of 650, adding into a reaction kettle (namely, the molar ratio is about 1.30), adding 3g of zinc acetate and 1.5g of Sb2O3 as catalysts, gradually heating to 245 ℃, starting transesterification, keeping 245 ℃ until the reaction system is homogeneous, and evaporating the glycol in the reaction system by adopting a vacuum distillation method until the evaporation amount of the glycol is close to a theoretical value, and evaporating 329g of the glycol from the reaction system. A polyetherester polyol having a molecular weight of 3450 was obtained. The polyether ester polyol has a viscosity of 1S -1 at 40 ℃ of 35.2Poise, an acid value of 0.3 and a pale yellow liquid at normal temperature.
EXAMPLE 6 preparation of polyether ester polyol having molecular weight of 3500
Firstly, crushing polyethylene terephthalate, taking 699g of crushed polyethylene terephthalate (PET) and 4800.2g of poly (1, 3-propylene glycol) (P3 OG 1000) with the number average molecular weight of 1000, adding into a reaction kettle (namely, the molar ratio is about 1.32), adding 3g of zinc acetate and 1.5g of Sb2O3 as catalysts, gradually heating to 250 ℃, starting transesterification, keeping the temperature at 250 ℃ until the reaction system is homogeneous, and evaporating glycol in the reaction system by adopting a vacuum distillation method until the evaporation amount of the glycol is close to a theoretical value, and evaporating 286g of glycol from the reaction system. A polyetherester polyol having a molecular weight of 3500 was obtained. The polyether ester polyol has a viscosity of 1S -1 at 40 ℃ of 28.5Poise, an acid value of 0.3 and a pale yellow liquid at normal temperature.
Example 7 preparation of polyetherester polyol having molecular weight 3480
Firstly, crushing polybutylene terephthalate, taking 1137.14g of crushed polybutylene terephthalate (PBT) and 4362.85g of polytetrahydrofuran (PTG 650) with the number average molecular weight of 650, adding into a reaction kettle (namely, the molar ratio is about 1.30), adding 3g of zinc acetate and 1.5g of Sb2O3 as catalysts, gradually heating to 260 ℃, starting transesterification, keeping the temperature at 260 ℃ until the reaction system is homogeneous, and evaporating glycol in the reaction system by adopting a vacuum distillation method until the evaporation amount of the glycol is close to a theoretical value, and evaporating 465g of butanediol from the reaction system. A polyetherester polyol having a molecular weight of 3480 was obtained. The polyether ester polyol has a viscosity of 1S -1 at 40 ℃ of 35.8Poise, an acid value of 0.3 and a pale yellow liquid at normal temperature.
Examples 8-10 below are polyether ester polyols for use in making polyurethane elastic fibers
Example 8 polyether ester polyol of example 1 for making polyurethane elastic fiber
100Kg of the polyether ester polyol prepared in example 1 is added into a reaction kettle which has been kept at a constant temperature of 45 ℃, stirring is started, the stirring speed is 150rpm, 31kg of diphenylmethane diisocyanate is added, and the temperature is raised to 90 ℃ after stirring for 5 min; the reaction was allowed to proceed at 90℃for 2 hours to give a prepolymer.
The prepolymer was cooled to 50℃and dissolved with 166.72kg of dimethylacetamide (DMAc), and then an amine solution containing 2.40kg of ethylenediamine and 0.29kg of diethylamine at a mass concentration of 3.2% was added thereto, and the stirring speed was increased to 300rpm, to conduct a chain extension reaction. After the chain extension reaction is completed, adding necessary antioxidants, dyeing aids and other assistants, and curing for 30 hours to obtain the spinning stock solution with the solid content of 35%. And (3) carrying out dry spinning on the stock solution to obtain the polyurethane elastic fiber PUU-3 with the denier of 40D.
Example 9 polyether ester polyol of example 6 for the preparation of polyurethane elastic fiber
100Kg of polyether ester polyol prepared in example 1 is added into a reaction kettle which is already kept at a constant temperature of 45 ℃, stirring is started, the stirring speed is 150rpm, 16.15kg of diphenylmethane diisocyanate is added, and the temperature is raised to 90 ℃ after stirring for 5 min; the reaction was allowed to proceed at 90℃for 2 hours to give a prepolymer.
The prepolymer was cooled to 50℃and dissolved with 147.82kg of dimethylacetamide (DMAc), and then an amine solution containing 2.13kg of ethylenediamine and 0.26kg of diethylamine at a mass concentration of 3.2% was added thereto, and the stirring speed was increased to 300rpm, to conduct a chain extension reaction. After the chain extension reaction is completed, adding necessary antioxidants, dyeing aids and other assistants, and curing for 30 hours to obtain the spinning stock solution with the solid content of 35%. And (3) carrying out dry spinning on the stock solution to obtain the polyurethane elastic fiber PUU-4 with the denier of 40D.
Example 10 polyether ester polyol of example 7 for making polyurethane elastic fiber
100Kg of the polyether ester polyol prepared in the example 1 is added into a reaction kettle which is already kept at a constant temperature of 45 ℃, stirring is started, the stirring speed is 150rpm, 16.20kg of diphenylmethane diisocyanate is added, and the temperature is raised to 90 ℃ after stirring for 5 min; the reaction was allowed to proceed at 90℃for 2 hours to give a prepolymer.
The prepolymer was cooled to 50℃and was dissolved with 147.89kg of dimethylacetamide (DMAc), and then an amine solution containing 2.14kg of ethylenediamine and 0.27kg of diethylamine at a mass concentration of 3.2% was added thereto, and the stirring speed was increased to 300rpm, to conduct a chain extension reaction. After the chain extension reaction is completed, adding necessary antioxidants, dyeing aids and other assistants, and curing for 30 hours to obtain the spinning stock solution with the solid content of 35%. And (3) carrying out dry spinning on the stock solution to obtain the polyurethane elastic fiber PUU-5 with the denier of 40D.
Comparative example 1 Polytetrahydrofuran (PTMG) with number average molecular weight of 2000 for the preparation of polyurethane elastic fiber
100Kg of PTMG2000 (number average molecular weight 2000) was charged into a reaction vessel which had been thermostatted to 45℃and stirring was started at a stirring speed of 150rpm. 22.2kg of diphenylmethane diisocyanate was added, stirred for 5 minutes, then heated to 90℃and reacted at 90℃for 2 hours to give a prepolymer.
The prepolymer was cooled to 50℃and dissolved with 155.5kg of dimethylacetamide (DMAc), and then an amine solution containing 2.26kg of ethylenediamine and 0.28kg of diethylamine at a concentration of 3.2% was added thereto, and the stirring speed was increased to 300rpm, to conduct a chain extension reaction. After the chain extension reaction is completed, adding necessary antioxidants, dyeing aids and other assistants, and curing for 30 hours to obtain the spinning stock solution with the solid content of 35%. And (3) carrying out dry spinning on the stock solution to obtain the polyurethane elastic fiber PUU-0 with the denier of 40D.
Comparative example 2 polyethylene glycol having a number average molecular weight of 1500 was used to prepare polyurethane elastic fiber
100Kg of polyethylene glycol having a number average molecular weight of 1500 was added to a reaction vessel which had been thermostatted to 45℃and stirring was started at a stirring speed of 150rpm. 26.5kg of diphenylmethane diisocyanate was added, stirred for 5min and then heated to 90 ℃; this was reacted at 90℃for 2 hours to obtain a prepolymer.
The prepolymer was cooled to 50℃and dissolved with 161kg of dimethylacetamide (DMAc), and then an amine solution having a concentration of 3.2% containing 2.32kg of ethylenediamine and 0.28kg of diethylamine was added thereto, and the stirring speed was increased to 300rpm, to conduct a chain extension reaction. After the chain extension reaction is completed, adding necessary antioxidants, dyeing aids and other assistants, and curing for 30 hours to obtain the spinning stock solution with the solid content of 35%. And (3) carrying out dry spinning on the stock solution to obtain the polyurethane elastic fiber PUU-1 with the denier of 40D.
Comparative example 3 Polypropylene glycol with number average molecular weight of 2000 for the preparation of polyurethane elastic fiber
100Kg of polypropylene glycol having a number average molecular weight of 2000 was added to a reaction vessel which had been thermostatted to 45℃and stirring was started at a stirring speed of 150rpm. Adding 21.98kg of diphenylmethane diisocyanate, stirring for 5min, and heating to 90 ℃; this was reacted at 90℃for 2 hours to obtain a prepolymer.
The prepolymer was cooled to 50℃and was dissolved with 155.24kg of dimethylacetamide (DMAc), and then an amine solution having a concentration of 3.2% containing 2.24kg of ethylenediamine and 0.28kg of diethylamine was added thereto, and the stirring speed was increased to 300rpm, to conduct chain extension reaction. After the chain extension reaction is completed, adding necessary antioxidants, dyeing aids and other assistants, and curing for 30 hours to obtain the spinning stock solution with the solid content of 35%. And (3) carrying out dry spinning on the stock solution to obtain the polyurethane elastic fiber PUU-2 with the denier of 40D.
Comparative example 4 preparation of polyetherester polyol having molecular weight of 1200
Firstly, crushing polyethylene terephthalate, adding 2602.4g of crushed polyethylene terephthalate (PET) and 3000g of polyethylene glycol (PEG 200) with the number average molecular weight of 200 into a reaction kettle, adding 3g of zinc acetate and 1.5g of Sb2O3 serving as catalysts, gradually heating to 235 ℃, starting transesterification, maintaining 235 ℃ until the reaction system is homogeneous, evaporating ethylene glycol in the reaction system by adopting a vacuum distillation method, and evaporating 681g of ethylene glycol from the reaction system. Polyether ester diol with molecular weight of 1200 is obtained. The polyether ester diol is solid at 40 ℃, the melting point is 60 ℃, the acid value is 0.3, and the mol ratio of the ethylene glycol ester structure is 20%.
Comparative example 5 polyether ester polyol of comparative example 4 for preparing polyurethane elastic fiber
Adding 100kg of polyether ester polyol prepared in comparative example 4 into a reaction kettle which is already kept at a temperature of 90 ℃, starting stirring, adding 31kg of diphenylmethane diisocyanate at a stirring speed of 150rpm, and starting to perform a prepolymerization reaction; when the reaction proceeded to 57min, the prepolymer viscosity was too great to continue to complete the prepolymerization.
The following parameters of the polyurethane elastic fibers (i.e., spandex filaments) obtained in examples 8, 9, 10 and comparative examples 1,2, 3 were tested according to the above test methods, and the test results are summarized in the following tables.
As can be seen from the data in the table, compared with the polyurethane elastic fiber prepared from polyethylene glycol as a raw material, the polyurethane elastic fiber prepared from the polyether ester polyol has obviously improved tensile stress and breaking strength, and is close to or exceeds the polyurethane elastic fiber prepared from conventionally used polytetrahydrofuran ether glycol, so that the performance requirement of spandex filaments for clothing can be met; in addition, the plastic deformation rate of the polyurethane elastic fiber prepared by the polyether ester polyol is obviously reduced; from a value of 5UP200%, the polyurethane elastic fiber using the polyether ester diol of the present invention has a larger 5UP200% recovery stress, that is, has a larger recovery modulus, which indicates that the larger recovery force can make the fabric better in shape retention. In conclusion, the polyether ester polyol preparation method provided by the invention can use the post-consumer polyester as the raw material to prepare the polyether ester polyol raw material for spandex with performance similar to that of the conventional polytetrahydrofuran, and the prepared spandex has good mechanical property similar to that of the spandex prepared from polytetrahydrofuran, so that the wearability is effectively improved. Therefore, the polyether ester polyol prepared by the method for preparing polyether ester polyol by using polyester can be used as a soft segment raw material of spandex, so that the application path of the polyester recovery material is widened, and the raw material source of the spandex is also widened.
The spinning solutions in examples 8, 9, 10 and comparative examples 1, 2, 3 were diluted from 35% to 20% solids, and then polyurethane film gloves were prepared by dip-coating, and cut to obtain corresponding example film bars PUU-F3, PUU-F4, PUU-F5, and corresponding comparative example film bars PUU-F0, PUU-F1, PUU-F2. The specific preparation steps of the film sample strip are as follows:
firstly, slowly immersing a hand mould into a groove filled with diluted stock solution, then slowly lifting the hand mould out of the stock solution groove, slowly rotating the hand mould to ensure that the thickness of the stock solution on the surface of the hand mould is uniform, then drying the hand mould in an oven, and then taking down the glove after drying to obtain the polyurethane film glove with the wall thickness of about 150 micrometers. In order to test the mechanical properties of the glove film, the film on the palm portion of the glove was cut out and cut into strips with a width of 6mm and a length of 10cm, and the mechanical properties were tested.
The mechanical properties are as follows:
As can be seen from the data in the table, the film product glove prepared by using the polyether ester polyol disclosed by the invention has the advantages that the film cut from the palm is tested, and compared with the film prepared by using polyethylene glycol and polypropylene glycol as raw materials, the film prepared by using the polyether ester polyol has the advantages that the tensile stress and the breaking strength are obviously improved, the mechanical property of the film prepared by using the polyether ester polyol is similar to or exceeds that of the film prepared by using polytetrahydrofuran, the mechanical property requirement of the elastic film glove can be met, and the film is consistent with the phenomenon found by spandex filaments; meanwhile, the polyurethane film glove prepared from the polyether ester glycol prepared by the invention has the characteristic of low plastic deformation, so that the shape of the film glove product is more stable; from the value of 5UP200%, the polyurethane film membrane prepared by using the polyether ester glycol has larger 5UP200% restoring force, so that the glove coating property is better, and meanwhile, the glove can be made thinner on the premise of ensuring the coating force, so that the raw material cost of the film glove is reduced. The polyether ester polyol provided by the invention effectively improves the mechanical property of the membrane when the polyether ester polyol is used as a soft section of the polyurethane membrane fiber, on the basis, the thin-wall glove membrane product has lower shaping deformation rate and higher recovery modulus, the shape of the thin-wall glove product is kept, the coating property of the thin-wall glove product is improved, and the raw material production cost can be reduced.
Example 11 melt spun spandex made with polyetherester polyol of example 2
The polyether ester polyol, 1, 4-butanediol and diphenylmethane diisocyanate in the embodiment 2 are respectively metered into a double screw extruder according to the molar ratio of 1.2:2:3.2, are continuously polymerized and extruded at 195 ℃, are granulated underwater, are dried until the moisture content of polyurethane particles is lower than 100ppm, and are added with necessary additives such as an antioxidant, a light stabilizer and the like to be melt-spun together, so as to obtain the polyurethane TPU-1 with the denier of 20D.
Comparative example 6 melt spun spandex made from polytetrahydrofuran having a number average molecular weight of 2000
Polytetrahydrofuran PTMG2000 (with the number average molecular weight of 2000), 1, 4-butanediol and diphenylmethane diisocyanate are respectively metered into a double screw extruder according to the molar ratio of 1.2:2:3.2, are continuously polymerized and extruded at 190 ℃, are granulated under water, are dried until the moisture content of polyurethane particles is lower than 100ppm, and are added with necessary additives such as an antioxidant, a light stabilizer and the like to be melt-spun together, so that the TPU-0 with the denier of 20D is obtained.
Comparative example 7 melt spun spandex made with polyethylene glycol having a number average molecular weight of 1500
Polyethylene glycol with the number average molecular weight of 1500, 1, 4-butanediol and diphenylmethane diisocyanate are respectively metered into a double screw extruder according to the molar ratio of 1.2:2:3.2, continuously polymerized and extruded at 190 ℃, granulated underwater, dried until the moisture content of polyurethane particles is lower than 100ppm, and added with necessary additives such as an antioxidant, a light stabilizer and the like to be melt-spun together, thus obtaining the TPU-2 with the denier of 20D.
As can be seen from the comparison of the mechanical properties of the above comparative examples and examples, the melt-processed spandex filaments using polyetheresters as raw materials, which have significantly higher tensile stress and flexural modulus than melt-processed spandex filaments using polytetrahydrofuran, exhibit similar mechanical properties and advantages to melt-processed dry spandex filaments.

Claims (7)

1. A process for preparing a polyetherester polyol comprising the steps of:
step 1) adding polyether glycol and polyester as raw materials into a reaction kettle, wherein the polyester contains an aromatic dibasic acid polyol ester structure, the polymerization degree of the polyether glycol is 2-20, the molecular weight is 100-1000, and the molar ratio of the aromatic group structure in the polyether glycol and the polyester is more than 1.05:1;
and 2) heating the reaction kettle to a reaction temperature to perform transesterification, and evaporating micromolecular polyol produced by the transesterification by adopting a vacuum distillation method to prepare the polyether ester polyol, wherein the reaction temperature is higher than the boiling point of the micromolecular polyol and lower than the boiling point of the polyether glycol.
2. The method for preparing polyether ester polyol according to claim 1, wherein the polyether glycol is one or more of polyethylene glycol, poly-1, 3-propylene glycol, poly-1, 2-propylene glycol, polytetrahydrofuran, polyethylene glycol-1, 2-propylene glycol copolymer, polytetrahydrofuran-3-methyltetrahydrofuran copolymer.
3. The method of preparing a polyetherester polyol according to claim 1, wherein the molar ratio of aromatic group structures in the polyetherdiol and the polyester is calculated by the formula:
R＝(W+P-36)/(W-A)
In the method, in the process of the invention,
R is the mole ratio of polyether glycol to aromatic group structure in polyester,
W is the molecular weight of the target polyether ester polyol, and W is 1000-5000,
P is the molecular weight of aromatic dibasic acid in the polyester,
A is the average molecular weight of the polyether glycol.
4. The polyether ester polyol produced by the process for producing a polyether ester polyol according to claim 1, which comprises a structure and a terminal alcoholic hydroxyl group represented by the following formula (1) and the following formula (2):
Wherein R 1 is an aromatic group structure, the mass content of R 1 in the repeating unit of the formula (1) is 4.5-44%, R 2 is at least one of saturated alkane groups with 2-5 carbon atoms, x is 2-20, and R 3 is the residue of polyhydric alcohol in the polyester raw material;
The mass ratio of formula (2) in the structure of the polyetherester polyol is less than 20%, preferably less than 10%;
The polyether ester polyol has a number average molecular weight of 1000-5000;
The average functionality of the hydroxyl groups of the capped alcohol is from 1.95 to 2.00.
5. The polyether ester polyol according to claim 4, wherein R 2 is at least two of saturated alkane groups having 2 to 5 carbon atoms.
6. A method for producing polyurethane elastic fiber, nonwoven fabric, film or elastomer in a solution processing or melt processing manner using the polyetherester polyol produced by the method for producing polyetherester polyol according to any one of claims 1 to 3 or the polyetherester polyol according to claim 4 as a raw material.
7. A polyurethane elastic fiber, nonwoven, film or elastomer made according to the method of claim 6.
CN202310424908.4A 2023-04-18 2023-04-18 Method for preparing polyether ester polyol and product thereof Pending CN118496489A (en)

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CN202310424908.4A CN118496489A (en) 2023-04-18 2023-04-18 Method for preparing polyether ester polyol and product thereof
PCT/CN2024/088284 WO2024217450A1 (en) 2023-04-18 2024-04-17 Method for preparing polyether ester polyol and product thereof

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