CN112029083B - Polyether carbonate polyol and preparation method thereof - Google Patents

Polyether carbonate polyol and preparation method thereof Download PDF

Info

Publication number
CN112029083B
CN112029083B CN202010875376.2A CN202010875376A CN112029083B CN 112029083 B CN112029083 B CN 112029083B CN 202010875376 A CN202010875376 A CN 202010875376A CN 112029083 B CN112029083 B CN 112029083B
Authority
CN
China
Prior art keywords
glycol
polyol
catalyst
polyether carbonate
molecular weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010875376.2A
Other languages
Chinese (zh)
Other versions
CN112029083A (en
Inventor
秦玉升
古雅楠
辛志荣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yantai University
Original Assignee
Yantai University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yantai University filed Critical Yantai University
Priority to CN202010875376.2A priority Critical patent/CN112029083B/en
Publication of CN112029083A publication Critical patent/CN112029083A/en
Application granted granted Critical
Publication of CN112029083B publication Critical patent/CN112029083B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/305—General preparatory processes using carbonates and alcohols
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/183—Block or graft polymers containing polyether sequences
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/307—General preparatory processes using carbonates and phenols

Landscapes

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

Abstract

The invention provides polyether carbonate polyol and a preparation method thereof. Aiming at the problems that the cyclic carbonate is difficult to open the ring and the decarboxylation reaction is difficult to control, the preparation method effectively realizes the preparation of the polyether carbonate polyol with controllable carbonate unit content by combining the tin catalyst and the organic catalyst. The interaction of the organic catalyst with the metal catalyst, which effectively reduces the activation energy of the ring-opening polymerization reaction, is the main reason for achieving this process, and this interaction allows the reaction to occur at relatively low temperatures, thereby achieving effective control of carbonate content in the structure. The polyether carbonate polyol prepared by the method has the end group which is completely primary hydroxyl, and the content of carbon dioxide units in the structure is 15.2-35.5 wt%.

Description

Polyether carbonate polyol and preparation method thereof
Technical Field
The invention relates to the technical field of polymers, and particularly relates to polyether carbonate polyol and a preparation method thereof.
Background
Oligomer polyol is one of three main raw materials (oligomer polyol, isocyanate and chain extender) in the polyurethane material industry. According to the difference of the main chain structure, the oligomer polyols are mainly divided into three types of polyether polyols, polyester polyols and polycarbonate polyols, wherein the polyether polyol is used in the largest amount, and accounts for about 90 percent of the total amount of all polyols. The polyurethane using the polyether polyol as the raw material has better flexibility and low-temperature performance, and the ether bond is not easy to hydrolyze, so the hydrolysis resistance is better. Polyester and polycarbonate polyurethanes have good tensile properties, abrasion resistance and solvent resistance. How to prepare polyol materials with both advantages has been an important direction for the research of polyurethane industry. In recent years, much attention has been paid to the scientific research and industrial circles to the preparation of polyether carbonate polyol by a copolymerization method of carbon dioxide and epoxide, and the research mainly utilizes carbon dioxide and propylene oxide to synthesize polyol with a carbonate bond and an ether bond structure in the structure through copolymerization and telomerization under the condition of a double metal cyanide catalyst. For example, chinese patent application publication No. CN1060299A discloses the preparation of aliphatic poly (carbonate-ether) polyols, which is prepared by using a high polymer supported bimetallic catalyst to catalyze the reaction of carbon dioxide and epoxide to prepare poly (carbonate-ether) polyols with a carbonate content of less than 30%. Patents WO2012/163944, CN105542142B, CN102617844B, etc. also disclose methods for synthesizing polyether carbonate urethanes having different carbonate contents. The novel polyol material is mainly used for synthesizing polyurethane materials such as coatings, adhesives, leather slurry and the like.
However, the novel polyol using carbon dioxide as raw material also has many problems in application process, mainly including two aspects: (1) the polyol has poor reactivity, and because propylene oxide is mainly used as a raw material in the synthesis process, terminal hydroxyl of the prepared polyol is mainly secondary hydroxyl, so that the activity of the polyol is low when the polyol reacts with isocyanate, and the polyol is not ideal particularly when being applied to the fields of polyurethane foam and the like with high requirements on the activity. (2) The polyurethane material has insufficient performance, and the prepared polyurethane material has the problems of poor low-temperature resistance, insufficient toughness and the like due to higher glass transition temperature of the polyols, so the application range of the polyurethane material is greatly limited due to the problems. In addition, because the reaction uses low-boiling-point and flammable compounds such as propylene oxide and the like, the requirement on safety in the industrial production process is higher, and the production cost of materials is increased.
Disclosure of Invention
In view of the above problems, the present invention is directed to developing a novel polyether carbonate polyol and a method for preparing the same.
The invention provides polyether carbonate polyol which has the following structure:
Figure BDA0002651079800000021
x＝1-100，y＝1-100，
STA is a dehydrogenated group of an active hydrogen-containing initiator, preferably STA has the following aliphatic structure:
Figure BDA0002651079800000031
or STA has the following ester ring, aromatic ring structure:
Figure BDA0002651079800000032
or STA has the following aromatic structure:
Figure BDA0002651079800000033
or STA has the following branched structure:
Figure BDA0002651079800000034
or the STA has the following structure:
Figure BDA0002651079800000035
the polyether carbonate polyol prepared by the method has the advantages of low glass transition temperature and high reaction activity, the tensile property, wear resistance and solvent resistance of the polyurethane material prepared by using the polyether carbonate polyol are also obviously improved, the bottleneck problems that the market of the traditional polyol is saturated and limited in development, the glass transition temperature of the polyether carbonate is high, the reaction activity is low and the like are solved, and the development of the synthesis research of a novel polyurethane material is promoted.
The invention aims to realize the synthesis of polyether carbonate by utilizing the ring-opening polymerization of ethylene carbonate, wherein the ethylene carbonate can be prepared from carbon dioxide through a direct or indirect route or purchased from a commercial product, so the invention realizes the indirect utilization of the carbon dioxide and reduces the dependence of the polyol industry on traditional petrochemical resources. However, in the past research, the initiator is often petroleum-based polyol, and the method can utilize isosorbide as the initiator, so that the method is more in line with the green sustainable development concept. Furthermore, the invention also provides a preparation method of the polyether carbonate polyol, which comprises the following steps:
adding a tin-containing catalyst, an organic catalyst, an initiator and ethylene carbonate into a reactor according to a certain proportion, heating to 80-200 ℃ for reaction, and reacting for 2-60 hours under the stirring condition to obtain the polyether carbonate polyol.
Preferably, the tin-containing catalyst is one or more of stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic oxide, stannic myristate, stannic octoate, stannous benzoate, stannic stearate, tetraphenyltin, stannic alkoxide, stannic butoxide and other compounds.
Preferably, the organic catalyst is one or more of 1, 8-diazabicycloundecen-7-ene, diphenyl phosphine, tri-tert-butyl phosphine, triphenylphosphine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 4-dimethylaminopyridine, bistriphenylphosphine ammonium chloride, 6-caprolactam, 2-imidazolidinone, N-alkylimidazole, bipyridine, 4-pyrrolidinopyridine, phosphate ester, all-alkyl substituted triphosphazene, all-aryl substituted triphosphazene, proline and thiourea.
Preferably, the initiator is selected from one or more of small molecule alcohols, phenols, thiols, hydroxyl-containing oligomers.
Preferably, the small molecular alcohol is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butylene glycol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 6-hexanediol, octanediol, sebacic glycol, 1, 3-cyclopentanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, isosorbide, trimethylolethane, trimethylolpropane, glycerol, 1,2, 4-butanetriol, polyestertriol, or pentaerythritol;
preferably, the hydroxyl-containing oligomer is one or more of polyethylene glycol with a molecular weight of less than 2000, polypropylene glycol polybutylene adipate with a molecular weight of less than 2000, or polytetrahydrofuran diol with a molecular weight of less than 2000.
Preferably, the phenol is one or more of catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 4' -ethylene biphenol, bisphenol A, 4' - (2-methylpropylene) biphenol, 4- (2-ethylhexyl) biphenol and 2,2' -methylene biphenol;
preferably, the thiol is one or more of methyl mercaptan, dithiol or oligomeric polythiol.
Preferably, the molar ratio of the tin-containing catalyst to the organic catalyst is from 0.1 to 100: 1.
Preferably, the tin-containing catalyst is added in an amount of 0.01-5 wt% of the ethylene carbonate.
Preferably, the molar ratio of the ethylene carbonate to the initiator is 150-6: 1.
Aiming at the problems of poor reaction activity, higher glass transition temperature, safety in the preparation process and the like of the existing carbon dioxide-based polyol, the invention prepares the polyol material with high primary hydroxyl content and low glass transition temperature by utilizing the ring-opening polymerization of the ethylene carbonate. In general, a five-membered ring structure compound such as ethylene carbonate is chemically stable and is difficult to open a ring. The key point of the invention is that the activation energy of ring-opening polymerization reaction is reduced by the combination of tin catalyst and organic catalyst, thereby solving the difficult problems that the ring-opening of the cyclic carbonate is difficult and the decarboxylation reaction is difficult to control, realizing the control of the content of carbonate unit in a certain range, synthesizing the polyol material with primary hydroxyl as the end group and soft chain segment, and the polyether carbonate polyol prepared by the method has the advantages of low vitrification temperature and high reaction activity, and the tensile property, wear resistance and solvent resistance of the polyurethane material prepared by the polyether carbonate polyol are also obviously improved. Furthermore, the basic reason for the smooth preparation of the polyether carbonate polyol is that the organic catalyst and the metal catalyst interact to effectively reduce the activation energy of the ring-opening polymerization reaction, so that the ring-opening polymerization reaction of the ethylene carbonate can occur at a relatively low temperature (80-200 ℃), and the content of carbonate in the structure can be effectively controlled. In addition, the experimental result also proves that the polyether carbonate polyol with the terminal group completely being primary hydroxyl can be prepared, and the content of carbon dioxide unit in the structure is between 15.2wt% and 35.5 wt%.
Advantageous effects
The polyether carbonate polyol prepared by the invention has the end group which is completely primary hydroxyl, the content of carbon dioxide unit in the structure is between 15.2wt% and 35.5wt%, and the polyurethane material synthesized by the polyether carbonate polyol prepared by the invention has the advantages of low glass transition temperature (below minus 30 ℃) and good mechanical property.
The polyol of the invention selects relatively stable and safe cyclic carbonate as a raw material, and a polyol material with primary hydroxyl as a terminal group and soft chain segment is synthesized by a ring-opening polymerization method, thereby solving the bottleneck problems of saturated and limited market of the traditional polyol, high glass transition temperature of polyether carbonate, low reaction activity and the like.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
In order to further illustrate the present invention, a polyether carbonate polyol and a method for preparing the same according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
30.4g of the starter 1, 3-propanediol were charged into a 1L reaction flask equipped with a condenser and connected to a nitrogen blanket. 1g of a tin octylate catalyst and 0.15g of tri-tert-butylphosphine were added. 400g of ethylene carbonate are added with stirring. After replacing nitrogen for 3 times, the reaction flask is heated to 180 ℃ and reacted for 12 hours. Cooling to 100 ℃, decompressing and collecting unreacted ethylene carbonate ester to obtain a viscous polyether carbonate polyol product. The molecular weight of the polyether carbonate polyol was determined by GPC, the number average molecular weight was 1800, and the molecular weight distribution was 1.86. The product was titrated to a hydroxyl number of 59.5. The polyol obtained in this example had a carbon dioxide unit content of about 31.2 wt% as determined by nuclear magnetic resonance. Measured by the trifluoroacetate method19F-NMR spectrum analysis shows that the terminal hydroxyl groups are all primary hydroxyl groups. The DSC results showed a glass transition temperature of-21.2 ℃.
Example 2
48.5g of the starter polypropylene glycol (molecular weight 600) are introduced into a 1L reaction flask equipped with a condenser and connected to a nitrogen blanket. 0.5g of tin stearate catalyst and 0.32g of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene were added. 400g of ethylene carbonate are added with stirring. After replacing nitrogen for 3 times, the reaction flask was heated to 165 ℃ and reacted for 20 hours. Cooling to 100 ℃, decompressing and collecting unreacted ethylene carbonate ester to obtain a viscous polyether carbonate polyol product. The molecular weight of the polyether carbonate polyol was determined by GPC, the number average molecular weight was 2800, and the molecular weight distribution was 1.78. The product was titrated to a hydroxyl number of 42.5. The polyol obtained in this example had a carbon dioxide unit content of about 33.5% by weight as determined by nuclear magnetic resonance. DSC results showed a glass transition temperature of-20.0 ℃.
Example 3
8.0g of hydroquinone starting material was charged into a 1L reaction flask equipped with a condenser and connected to a nitrogen blanket. Adding 3g of stannous benzoate catalyst and 0.08g of ammonium bis (triphenylphosphine) chloride. 400g of ethylene carbonate are added with stirring. After replacing nitrogen for 3 times, the reaction flask is heated to 170 ℃ and reacted for 15 hours. Cooling to 100 ℃, decompressing and collecting unreacted ethylene carbonate ester to obtain a viscous polyether carbonate polyol product. The molecular weight of the polyether carbonate polyol was determined by GPC, with a number average molecular weight of 3600 and a molecular weight distribution of 1.48. The product was titrated to a hydroxyl number of 32.3. The polyol obtained in this example had a carbon dioxide unit content of about 25.8 wt% as determined by nuclear magnetic analysis. The DSC results showed a glass transition temperature of-25.6 ℃.
Example 4
25.6g of the initiator tripropylene glycol are charged into a 1L reaction flask equipped with a condenser tube and connected to a nitrogen blanket. Adding stannous octoate catalyst 0.04g and 6-caprolactam 0.15 g. 400g of ethylene carbonate are added with stirring. After replacing nitrogen for 3 times, the reaction flask is heated to 160 ℃ and reacted for 30 hours. Cooling to 100 ℃, decompressing and collecting unreacted ethylene carbonate ester to obtain a viscous polyether carbonate polyol product. The molecular weight of the polyether carbonate polyol was determined by GPC, the number average molecular weight was 1500, and the molecular weight distribution was 1.91. The product was titrated to a hydroxyl number of 76.5. The polyol obtained in this example had a carbon dioxide unit content of about 32.5% by weight as determined by nuclear magnetic resonance. The DSC results showed a glass transition temperature of-22.2 ℃.
Example 5
12.2g of the starting material isosorbide was charged into a 1L reaction flask equipped with a condenser tube and connected to a nitrogen blanket. Adding stannous octoate catalyst 1g and N-alkyl imidazole 0.15 g. 400g of ethylene carbonate are added with stirring. After replacing nitrogen for 3 times, the reaction flask is heated to 180 ℃ and reacted for 8 hours. Cooling to 100 ℃, and collecting unreacted ethylene carbonate under reduced pressure to obtain a viscous polyether carbonate polyol product. The molecular weight of the polyether carbonate polyol was determined by GPC, the number average molecular weight was 2500, and the molecular weight distribution was 1.53. The product was titrated to a hydroxyl number of 45.3. The polyol obtained in this example had a carbon dioxide unit content of about 25.3 wt% as determined by nuclear magnetic analysis. The DSC results showed a glass transition temperature of-28.2 ℃.
Example 6
5.0g of the starting pentaerythritol were charged into a 1L reaction flask equipped with a condenser and connected to a nitrogen blanket. Adding stannous octoate catalyst 1g, 4-dimethylamino pyridine 0.30 g. 400g of ethylene carbonate are added with stirring. After replacing nitrogen for 3 times, the reaction flask was heated to 175 ℃ and reacted for 16 hours. Cooling to 100 ℃, decompressing and collecting unreacted ethylene carbonate ester to obtain a viscous polyether carbonate polyol product. The molecular weight of the polyether carbonate polyol was determined by GPC, with a number average molecular weight of 3000 and a molecular weight distribution of 1.75. The product was titrated to a hydroxyl number of 75.5. The polyol obtained in this example had a carbon dioxide unit content of about 28.9 wt% as determined by nuclear magnetic analysis. The DSC results showed a glass transition temperature of-25.6 ℃.
Example 7
22.5g of the starting bisphenol A are introduced into a 1L reaction flask equipped with a condenser and connected to a nitrogen blanket. 5g of tin octoate catalyst and 0.52g of 2-imidazolidinone were added. 400g of ethylene carbonate are added with stirring. After replacing nitrogen for 3 times, the reaction flask is heated to 170 ℃ and reacted for 12 hours. Cooling to 100 ℃, decompressing and collecting unreacted ethylene carbonate ester to obtain a viscous polyether carbonate polyol product. The molecular weight of the polyether carbonate polyol was determined by GPC, the number average molecular weight was 2010, and the molecular weight distribution was 1.80. The product was titrated to a hydroxyl number of 54.5. The polyol obtained in this example had a carbon dioxide unit content of about 35.5wt% as determined by nuclear magnetic analysis. The DSC results showed a glass transition temperature of-15.2 ℃.
Example 8
14.5g of the initiator tripropylene glycol are charged into a 1L reaction flask equipped with a condenser tube and connected to a nitrogen blanket. Adding 3g of stannous benzoate catalyst and 0.08g of ammonium bis (triphenylphosphine) chloride. 400g of ethylene carbonate are added with stirring. After replacing nitrogen for 3 times, the reaction flask is heated to 200 ℃ and reacted for 6 hours. Cooling to 100 ℃, and collecting unreacted ethylene carbonate under reduced pressure to obtain a viscous polyether carbonate polyol product. The molecular weight of the polyether carbonate polyol was determined by GPC, with a number average molecular weight of 2600 and a molecular weight distribution of 1.46. The product was titrated to a hydroxyl number of 46.5. The polyol obtained in this example had a carbon dioxide unit content of about 15.2wt% as determined by nuclear magnetic analysis. The DSC results showed a glass transition temperature of-32.2 ℃.
Example 9
11.8g of the initiator tripropylene glycol is charged into a 1L reaction flask equipped with a condenser and connected to a nitrogen blanket. 2g of a tin stearate catalyst and 0.13g of ammonium bis (triphenylphosphine) chloride were added. 400g of ethylene carbonate are added with stirring. After replacing nitrogen for 3 times, the reaction flask is heated to 190 ℃ and reacted for 10 hours. Cooling to 100 ℃, decompressing and collecting unreacted ethylene carbonate ester to obtain a viscous polyether carbonate polyol product. The molecular weight of the polyether carbonate polyol was determined by GPC, the number average molecular weight was 3400, and the molecular weight distribution was 1.68. The product was titrated to a hydroxyl number of 59.5. The polyol obtained in this example had a carbon dioxide unit content of about 20.6 wt% as determined by nuclear magnetic analysis. The DSC results showed a glass transition temperature of-29.5 ℃.
Example 10
6.0g of the initiator phloroglucinol was charged into a 1L reaction flask equipped with a condenser tube and connected to a nitrogen blanket. Adding stannous chloride catalyst 1g and tetrabutyl ammonium bromide 0.20 g. 400g of ethylene carbonate are added with stirring. After replacing nitrogen for 3 times, the reaction flask is heated to 170 ℃ and reacted for 18 hours. Cooling to 100 ℃, decompressing and collecting unreacted ethylene carbonate ester to obtain a viscous polyether carbonate polyol product. The molecular weight of the polyether carbonate polyol was determined by GPC, with a number average molecular weight of 5000 and a molecular weight distribution of 1.62. The product was titrated to a hydroxyl number of 34.0. The polyol obtained in this example had a carbon dioxide unit content of about 29.8 wt% as determined by nuclear magnetic analysis. The DSC results showed a glass transition temperature of-23.2 ℃.
The following examples, which use commercially available polypropylene glycol (PPG) as a reference and the polyether carbonate polyols prepared in examples 1 and 5 as application examples, demonstrate that the polyurethane materials prepared using the polyether carbonate polyols of the present invention as a raw material have better mechanical properties.
Reference example 1
Commercially available polypropylene glycol (PPG) (molecular weight 2000), 1, 4-butanediol were added to the reactor and heated to 120 ℃ with stirring to remove water. 20ppm of dibutyltin dilaurate were added as catalyst. 4,4' -diphenylmethane diisocyanate (MDI) heated to 100 ℃ is added in one portion with stirring. The reaction temperature reached about 190 ℃ until the maximum possible torque of the stirrer was reached. The reaction mixture was then poured onto a mold and aged at 80 ℃ for 30 minutes. After cooling, an elastomeric sheet 1 is obtained. According to the test of GB/T1040-2006, the tensile strength is 23.5MPa, and the elongation at break is 669%. The water absorption rate is about 3 percent when the fabric is soaked in water for 1 week at room temperature.
Application example 1
1.0mol (molecular weight 1800) of the polyol prepared in example 1 and 1.0mol of 1, 4-butanediol were added to the reactor and heated to 120 ℃ with stirring to remove water. 20ppm of dibutyltin dilaurate were added as catalyst. 2.0mol of 4,4' -diphenylmethane diisocyanate (MDI) heated to 100 ℃ are added in one portion with stirring. The reaction temperature reached approximately 195 ℃ until the maximum possible torque of the stirrer was reached. The reaction mixture was then poured onto a mold and aged at 80 ℃ for 30 minutes. After cooling, an elastomeric sheet 2 is obtained. According to the test of GB/T1040-. Soaking in water at room temperature for 1 week, and the water absorption is lower than 0.8%.
Application example 2
1.0mol (molecular weight 2500) of the polyol prepared in example 5 and 1.0mol of 1, 4-butanediol were charged into a reactor and heated to 120 ℃ with stirring to remove water. 20ppm of dibutyltin dilaurate were added as catalyst. 2.0mol of 4,4' -diphenylmethane diisocyanate (MDI) heated to 100 ℃ are added in one portion with stirring. The reaction temperature reached approximately 195 ℃ until the maximum possible torque of the stirrer was reached. The reaction mixture was then poured onto a mold and aged at 80 ℃ for 30 minutes. After cooling, an elastomeric sheet 3 is obtained. According to the test of GB/T1040-2006, the tensile strength is 42.8MPa, and the breaking elongation is 692%. Soaking in water at room temperature for 1 week, and the water absorption is lower than 1.0%.
The demonstration of the examples 1 to 10 shows that the polyether carbonate polyol prepared by the ring-opening method of the cyclic carbonate is completely primary hydroxyl, the content of carbon dioxide units in the structure is between 15.2wt% and 35.5wt%, the glass transition temperature is lower (can reach below-30 ℃), and the bottleneck problems of high glass transition temperature and low reaction activity of the conventional polyether carbonate are solved. Furthermore, the tests of the comparative example and the application example show that the tensile property, the abrasion resistance and the solvent resistance of the polyurethane material prepared by using the polyether carbonate polyol as the raw material are also obviously improved, a new structure polyol raw material is provided for polyurethane and other industries, the possibility is provided for preparing a new performance polyurethane material, and the problems of saturated market, low product added value and the like of the traditional polyol at present are favorably solved. The invention has the outstanding substantive characteristics that the activation energy of ring-opening polymerization reaction is reduced by the method of combining the tin catalyst and the organic catalyst, the problems that the ring-opening of the cyclic carbonate is difficult and the decarboxylation reaction is difficult to control are solved, the polyol material with primary hydroxyl as the end group and soft chain segment is synthesized, and the carbonate unit content in the preparation method can be controlled in a certain range.
Therefore, the test results of the examples and the application examples prove that the polyether carbonate polyol with the terminal group completely being a primary hydroxyl group can be prepared, and the prepared polyether carbonate polyol has the advantages of low glass transition temperature and high reactivity, and the polyurethane elastomer material prepared from the polyether carbonate polyol also has excellent tensile property, wear resistance, hydrolytic stability and solvent resistance.
Although the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the details of the embodiments, and various equivalent modifications can be made within the technical spirit of the present invention, and the scope of the present invention is also within the scope of the present invention. It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.

Claims (4)

1. A method for preparing polyether carbonate polyol, which is characterized by comprising the following steps:
adding a tin-containing catalyst, an organic catalyst, an initiator and ethylene carbonate into a reactor according to a certain proportion, and heating to 80-200 DEG CoC, reacting for 2-60 hours under the stirring condition to obtain polyether carbonate polyol;
the stanniferous catalyst is one or more of stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic oxide, stannic myristate, stannic octoate, stannous benzoate, stannic stearate, tetraphenyltin, stannic alkoxide and stannic butoxide;
the organic catalyst is one or more of 1, 8-diazabicycloundecen-7-ene, diphenylphosphine, tri-tert-butylphosphine, triphenylphosphine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 4-dimethylaminopyridine, bistriphenylphosphine ammonium chloride, 6-caprolactam, 2-imidazolidinone, N-alkylimidazole, bipyridine, 4-pyrrolidinopyridine, phosphate, all-alkyl substituted triphosphazene, all-aryl substituted triphosphazene, proline and thiourea;
the initiator is selected from one or more of small molecular alcohol, phenol, mercaptan and oligomer containing hydroxyl,
wherein the small molecular alcohol is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butylene glycol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 6-hexanediol, octanediol, sebacic glycol, 1, 3-cyclopentanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, isosorbide, trimethylolethane, trimethylolpropane, glycerol, 1,2, 4-butanetriol, polyestertriol or pentaerythritol,
the oligomer containing hydroxyl is one or more of polyethylene glycol with molecular weight lower than 2000, polypropylene glycol polybutylene adipate with molecular weight lower than 2000 or polytetrahydrofuran diol with molecular weight lower than 2000,
the phenol is one or more of catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 4' -ethylene biphenol, bisphenol A, 4' - (2-methylpropylidene) biphenol, 4- (2-ethylhexyl) biphenol and 2,2' -methylene biphenol,
the thiol is one or more of methyl mercaptan, dithiol or oligomeric polythiol.
2. The method according to claim 1, wherein the molar ratio of the tin-containing catalyst to the organic catalyst is 0.1 to 100: 1.
3. The method of claim 1, wherein the tin-containing catalyst is added in an amount of 0.01wt% to 5wt% of the ethylene carbonate.
4. The method according to claim 1, wherein the molar ratio of the ethylene carbonate to the initiator is 150 to 6: 1.
CN202010875376.2A 2020-08-26 2020-08-26 Polyether carbonate polyol and preparation method thereof Active CN112029083B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010875376.2A CN112029083B (en) 2020-08-26 2020-08-26 Polyether carbonate polyol and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010875376.2A CN112029083B (en) 2020-08-26 2020-08-26 Polyether carbonate polyol and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112029083A CN112029083A (en) 2020-12-04
CN112029083B true CN112029083B (en) 2022-06-24

Family

ID=73581668

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010875376.2A Active CN112029083B (en) 2020-08-26 2020-08-26 Polyether carbonate polyol and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112029083B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113773483A (en) * 2021-09-03 2021-12-10 山东一诺威新材料有限公司 Carbon dioxide-based polycarbonate ether polyol for slow-rebound polyurethane foam and preparation method thereof
CN115028845B (en) * 2022-05-11 2023-05-12 烟台大学 Zinc coordination polymer catalyst and preparation method and application thereof
CN114805781B (en) * 2022-05-20 2023-10-27 烟台大学 Poly (carbonate-ether) polyol and preparation method thereof
CN114957674B (en) * 2022-06-22 2023-06-23 烟台大学 Organosilicon polyol and preparation method thereof
CN115785431A (en) * 2022-11-23 2023-03-14 杭州普力材料科技有限公司 Polyether polyol containing carbamate structure and synthesis method and application thereof
CN116003768B (en) * 2023-03-03 2023-07-18 广东吉美帮新材料有限公司 Method for producing polycarbonate polyol by taking carbon dioxide as raw material
CN116970158A (en) * 2023-09-25 2023-10-31 山东尚正新材料科技股份有限公司 Process for preparing polypropylene carbonate diol

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101633731B (en) * 2009-08-14 2011-08-03 广州市达志化工科技有限公司 Preparation method of aliphatic polycarbonate polybasic alcohol
CN101701062A (en) * 2009-11-17 2010-05-05 常州化学研究所 Method for synthesizing aliphatic polycarbonate polyols
CN101775129B (en) * 2010-02-04 2012-06-27 东南大学 Method for preparing polyether carbonate polyol
DE102010008410A1 (en) * 2010-02-18 2011-08-18 Bayer MaterialScience AG, 51373 Process for the preparation of polyethercarbonate polyols
EP2441788A1 (en) * 2010-10-14 2012-04-18 Bayer MaterialScience AG Method for manufacturing polyether polyols
EP2730602A1 (en) * 2012-11-09 2014-05-14 Bayer MaterialScience AG Method for manufacturing polyether carbonate polyols
KR20150084820A (en) * 2012-11-09 2015-07-22 바이엘 머티리얼사이언스 아게 Method for producing polyether carbonate polyols
JP6804468B2 (en) * 2015-04-29 2020-12-23 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ Mixture of polyether carbonate polyol and polyether polyol for producing flexible polyurethane foam

Also Published As

Publication number Publication date
CN112029083A (en) 2020-12-04

Similar Documents

Publication Publication Date Title
CN112029083B (en) Polyether carbonate polyol and preparation method thereof
AU2014214024A1 (en) Synthesis of polyurethane polymers via copper azide-alkyne click chemistry for coatings, adhesives, sealants and elastomer applications
EP0471765B1 (en) Polyester chain-extended vinyl ether urethane oligomers
TW200904852A (en) Process for producing polyol and the polyol
WO2013157486A1 (en) Method for producing polyether
JP2008505230A (en) Oligocarbonate polyols containing terminal secondary hydroxyl groups
CN113563588A (en) Hydroxyl-terminated siloxane, silicon polyurethane containing same and preparation method thereof
CN114149576A (en) Fluorine-containing polycarbonate diol and preparation method thereof
CN102471444A (en) Process for preparing polyurethane polymers comprising polyester polyols having secondary hydroxyl end groups
EP4132989B1 (en) Thermoplastic polyurethanes derived from lignin monomers
CN109721701A (en) A kind of thermoplastic urethane elastomer composition and preparation method and purposes
JP3985264B2 (en) Method for producing highly functional polycarbonate polyol
JP4273876B2 (en) Polyether monool or polyether polyol and method for producing the same
CN115286764B (en) Nonionic waterborne polyurethane and preparation method and application thereof
US5284980A (en) Block copolyethers via oxonium coupling of poly(tetramethylene ether) glycols
CN109021196B (en) Organic silicon type polyurethane damping material and preparation method thereof
JP5446798B2 (en) Chlorinated polyether composition and method for producing the same
CN110256662B (en) Preparation method of low-molecular-weight aliphatic polycarbonate polyol
JP2021185219A (en) Hydrophilic urethane-based water sealing agent
JP5521213B2 (en) Chlorinated polyether copolymer and process for producing the same
EP0508119B1 (en) Novel process for the preparation of amine-terminated compounds
CN114262420B (en) Preparation method of recyclable bio-based polyester polyurethane
JPWO2014073580A1 (en) Method for producing hydroxyl group-containing polyether, method for producing hydrolyzable silyl group-containing polyether, and method for producing urethane prepolymer
US5055496A (en) Polymer product containing isobutylene oxide polyols
WO2011040418A1 (en) Method for manufacturing an isocyanate-terminated prepolymer, prepolymer obtained thereby, and polyurethane resin

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant