CN111138632A - Production method of bio-based solvent-free polyurethane - Google Patents

Production method of bio-based solvent-free polyurethane Download PDF

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Publication number
CN111138632A
CN111138632A CN201911320210.8A CN201911320210A CN111138632A CN 111138632 A CN111138632 A CN 111138632A CN 201911320210 A CN201911320210 A CN 201911320210A CN 111138632 A CN111138632 A CN 111138632A
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CN
China
Prior art keywords
bio
free polyurethane
agent
mixture
based solvent
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.)
Pending
Application number
CN201911320210.8A
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Chinese (zh)
Inventor
黄小平
戴启彬
黄明珠
张嘉栋
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.)
Fujian Xiaowei Jinshi Technology Incubation Co ltd
Fujian Chengjie Polymer Material Co ltd
Original Assignee
Fujian Xiaowei Jinshi Technology Incubation Co ltd
Fujian Chengjie Polymer Material Co ltd
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Application filed by Fujian Xiaowei Jinshi Technology Incubation Co ltd, Fujian Chengjie Polymer Material Co ltd filed Critical Fujian Xiaowei Jinshi Technology Incubation Co ltd
Priority to CN201911320210.8A priority Critical patent/CN111138632A/en
Publication of CN111138632A publication Critical patent/CN111138632A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/77Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78Nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269Lactones
    • C08G18/4277Caprolactone and/or substituted caprolactone
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633Compounds of group C08G18/42
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633Compounds of group C08G18/42
    • C08G18/6637Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633Compounds of group C08G18/42
    • C08G18/6637Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648Compounds 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
    • C08G18/6655Compounds 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 C08G18/3271

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

Abstract

The invention discloses a production method of bio-based solvent-free polyurethane, which comprises the following steps: s1: adding the bio-based polymer, polycaprolactone, amino acid diisocyanate, a processing agent, an auxiliary agent and auxiliary materials into a reaction kettle, and uniformly stirring to obtain a mixture; s2: and detecting the obtained mixture, after the obtained mixture is qualified through inspection, filtering and packaging, subpackaging and storing according to weight, wherein the viscosity of the bio-based polymer is less than 3000mPa.s, the content of the bio-based raw material is more than 60 percent, the bio-based raw material is one or more than two of Sovermol1092, Sovermol810 and Sovermol760, the bio-based raw material is mixed according to any ratio and does not contain a solvent, the amino acid diisocyanate is lysine diisocyanate or L-lysine diisocyanate and is a degradable and nontoxic material, and the processing agent comprises a cross-linking agent and a chain extender. The production method of the bio-based solvent-free polyurethane can improve the reaction effect and efficiency and improve the overall quality.

Description

Production method of bio-based solvent-free polyurethane
Technical Field
The invention belongs to the technical field of polyurethane production, and particularly relates to a production method of bio-based solvent-free polyurethane.
Background
Polyurethane is short for polyurethane, and is called polyurethane in English, which is a high molecular material. Polyurethane is a new organic polymer material, is known as 'fifth major plastic', and is widely applied to various fields of national economy due to excellent performance. Polyurethane is a high molecular material. The coating can be widely applied to daily life such as paint and coating in furniture, refrigerators and freezers in household appliances, roof waterproof heat-insulating layers and inner and outer wall coatings in the building industry and the like. Can also be made into various polyurethane materials such as polyurethane soles, polyurethane fibers, polyurethane sealant and the like. Generally speaking, the polyurethane product has wide adjustable range of performance, strong adaptability, biological aging resistance and moderate price, and the production efficiency of the bio-based polyurethane production is reduced, thereby influencing the normal production requirement.
Therefore, in order to meet the current situation, the design and production method of bio-based solvent-free polyurethane are urgently needed to meet the requirement of practical use.
Disclosure of Invention
The invention aims to provide a production method of bio-based solvent-free polyurethane, which solves the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a method for producing bio-based solvent-free polyurethane comprises the following steps:
s1: adding the bio-based polymer, polycaprolactone, amino acid diisocyanate, a processing agent, an auxiliary agent and auxiliary materials into a reaction kettle, and uniformly stirring to obtain a mixture;
s2: and detecting the obtained mixture, filtering and packaging after the mixture is qualified, and subpackaging and storing according to the weight.
Preferably, the viscosity of the bio-based polymer is less than 3000mPa.s, the content of the bio-based raw material is more than 60%, and the bio-based raw material is one or more than two of Sovermol1092, Sovermol810 and Sovermol760 which are mixed according to any ratio and do not contain solvent.
Preferably, the amino acid diisocyanate is lysine diisocyanate or L-lysine diisocyanate, and both are degradable and nontoxic materials.
Preferably, the processing agent comprises a cross-linking agent and a chain extender, wherein the cross-linking agent is one or a mixture of more than one of glycerol, trimethylolpropane, pentaerythritol, triethanolamine and diethanolamine.
Preferably, the chain extender is one or a mixture of more than two of 3, 3-dichloro-4, 4-diphenylmethane diamine, 3, 5-dimethylthiotoluene diamine, 3, 5-diethyltoluene diamine, ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, dipropylene glycol and 1, 3-pentanediol.
Preferably, the auxiliary agent comprises a dispersing agent and a leveling agent, the dispersing agent is polyacrylic acid ammonium salt, an organic silicon surfactant or polyether siloxane copolymer, and the leveling agent is polyether polyurethane, polyether modified polydimethylsiloxane or polyester modified polydimethylsiloxane.
Preferably, the auxiliary material is a catalyst and a coupling agent, the catalyst is one or a mixture of more than one of an organic tin catalyst, an organic bismuth catalyst and a tertiary amine catalyst, and the coupling agent is gamma-23-glycidoxypropyltrimethoxysilane.
Preferably, the rotation speed of the stirring is set to 200-300 revolutions per minute, the stirring temperature is set to 40-60 ℃, and the stirring time is set to 6-12 minutes.
Preferably, the mesh number of the filtering net is set to be 120 meshes, and the material of the filtering net is set to be a material which does not react with the mixture.
The invention has the technical effects and advantages that: according to the production method of the bio-based solvent-free polyurethane, the arrangement of the cross-linking agent and the chain extender can improve the overall reaction speed and the overall effect, and the arrangement of the catalyst can improve the overall reaction efficiency; the dispersing agent and the leveling agent can improve the effect of the mixture after reaction and improve the overall quality of the mixture; the filtering of the mixture can improve the overall fineness and the overall quality, and the production method of the bio-based solvent-free polyurethane can improve the reaction effect and efficiency and improve the overall quality.
Detailed Description
The technical solutions in the present disclosure will be clearly and completely described below with reference to the present disclosure, and it is obvious that the described contents are only a part of the present disclosure, and not all of the present disclosure. All other matters which can be obtained by a person skilled in the art without making creative efforts based on the contents of the present invention belong to the protection scope of the present invention.
The invention provides a production method of bio-based solvent-free polyurethane, which comprises the following steps:
s1: adding the bio-based polymer, polycaprolactone, amino acid diisocyanate, a processing agent, an auxiliary agent and auxiliary materials into a reaction kettle, and uniformly stirring to obtain a mixture;
s2: and detecting the obtained mixture, filtering and packaging after the mixture is qualified, and subpackaging and storing according to the weight.
Specifically, the viscosity of the bio-based polymer is less than 3000mPa.s, the content of the bio-based raw material is more than 60%, and the bio-based raw material is one or more than two of Sovermol1092, Sovermol810 and Sovermol760 which are mixed according to any ratio and do not contain solvents.
Specifically, the amino acid diisocyanate is lysine diisocyanate or L-lysine diisocyanate, and is a degradable and nontoxic material.
Specifically, the processing agent comprises a cross-linking agent and a chain extender, wherein the cross-linking agent is one or a mixture of more than one of glycerol, trimethylolpropane, pentaerythritol, triethanolamine and diethanolamine.
Specifically, the chain extender is one or a mixture of more than two of 3, 3-dichloro-4, 4-diphenylmethane diamine, 3, 5-dimethylthiotoluene diamine, 3, 5-diethyltoluene diamine, ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, dipropylene glycol and 1, 3-pentanediol.
Specifically, the auxiliary agent comprises a dispersing agent and a leveling agent, the dispersing agent is polyacrylic acid ammonium salt, an organic silicon surfactant or polyether siloxane copolymer, and the leveling agent is polyether polyurethane, polyether modified polydimethylsiloxane or polyester modified polydimethylsiloxane.
Specifically, the auxiliary material is a catalyst and a coupling agent, the catalyst is one or a mixture of more than one of an organic tin catalyst, an organic bismuth catalyst and a tertiary amine catalyst, and the coupling agent is gamma-23-glycidoxypropyltrimethoxysilane.
Specifically, the rotation speed of the stirring is set to 200-300 revolutions per minute, the stirring temperature is set to 40-60 ℃, and the stirring time is set to 6-12 minutes.
Specifically, the mesh number of the filtering net is set to be 120 meshes, and the material of the filtering net is set to be a material which does not react with the mixture.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing description, it will be apparent to one skilled in the art that various changes, modifications, equivalents, and improvements may be made without departing from the spirit and scope of the invention.

Claims (9)

1. A production method of bio-based solvent-free polyurethane is characterized in that: the method comprises the following steps:
s1: adding the bio-based polymer, polycaprolactone, amino acid diisocyanate, a processing agent, an auxiliary agent and auxiliary materials into a reaction kettle, and uniformly stirring to obtain a mixture;
s2: and detecting the obtained mixture, filtering and packaging after the mixture is qualified, and subpackaging and storing according to the weight.
2. The method of claim 1 for producing a bio-based solvent-free polyurethane, wherein: the viscosity of the bio-based polymer is less than 3000mPa.s, the content of the bio-based raw material is more than 60%, the bio-based raw material is one or more than two of Sovermol1092, Sovermol810 and Sovermol760, and the bio-based polymer is mixed according to any ratio and does not contain a solvent.
3. The method for producing bio-based solvent-free polyurethane according to claim 1, wherein said amino acid diisocyanate is lysine diisocyanate or L-lysine diisocyanate, and both are degradable and non-toxic materials.
4. The method of claim 1 for producing a bio-based solvent-free polyurethane, wherein: the processing agent comprises a cross-linking agent and a chain extender, wherein the cross-linking agent is one or a mixture of more than one of glycerol, trimethylolpropane, pentaerythritol, triethanolamine and diethanolamine.
5. The method for producing bio-based solvent-free polyurethane according to claim 4, wherein: the chain extender is one or a mixture of more than two of 3, 3-dichloro-4, 4-diphenylmethane diamine, 3, 5-dimethylthio toluene diamine, 3, 5-diethyl toluene diamine, ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, dipropylene glycol and 1, 3-pentanediol.
6. The method of claim 1 for producing a bio-based solvent-free polyurethane, wherein: the auxiliary agent comprises a dispersing agent and a leveling agent, wherein the dispersing agent is polyacrylic acid ammonium salt, an organic silicon surfactant or polyether siloxane copolymer, and the leveling agent is polyether polyurethane, polyether modified polydimethylsiloxane or polyester modified polydimethylsiloxane.
7. The method of claim 1 for producing a bio-based solvent-free polyurethane, wherein: the auxiliary material is a catalyst and a coupling agent, the catalyst is one or a mixture of more than one of an organic tin catalyst, an organic bismuth catalyst and a tertiary amine catalyst, and the coupling agent is gamma-23-glycidoxypropyltrimethoxysilane.
8. The method of claim 1 for producing a bio-based solvent-free polyurethane, wherein: the stirring speed is set to be 200-300 revolutions per minute, the stirring temperature is set to be 40-60 ℃, and the stirring time is set to be 6-12 minutes.
9. The method of claim 1 for producing a bio-based solvent-free polyurethane, wherein: the mesh number of the filtering net is set to be 120 meshes, and the material of the filtering net is set to be a material which does not react with the mixture.
CN201911320210.8A 2019-12-19 2019-12-19 Production method of bio-based solvent-free polyurethane Pending CN111138632A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012062370A (en) * 2010-09-14 2012-03-29 Bridgestone Corp Biodegradable polyurethane
CN108059706A (en) * 2017-12-18 2018-05-22 苏州浩洋聚氨酯科技有限公司 Biodegradable polyurethane and preparation method thereof
CN108276551A (en) * 2017-12-26 2018-07-13 合肥科天水性科技有限责任公司 A kind of multiple cross-linked modified aqueous polyurethane resin of biology base and its preparation method and application
CN109438653A (en) * 2018-10-26 2019-03-08 万华化学集团股份有限公司 A kind of bion thermoplastic polyurethane elastomer and preparation method thereof
CN109504266A (en) * 2018-10-18 2019-03-22 信和新材料股份有限公司 A kind of quick-drying no-solvent polyurethane paint and preparation method thereof modified based on bio-based polymers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012062370A (en) * 2010-09-14 2012-03-29 Bridgestone Corp Biodegradable polyurethane
CN108059706A (en) * 2017-12-18 2018-05-22 苏州浩洋聚氨酯科技有限公司 Biodegradable polyurethane and preparation method thereof
CN108276551A (en) * 2017-12-26 2018-07-13 合肥科天水性科技有限责任公司 A kind of multiple cross-linked modified aqueous polyurethane resin of biology base and its preparation method and application
CN109504266A (en) * 2018-10-18 2019-03-22 信和新材料股份有限公司 A kind of quick-drying no-solvent polyurethane paint and preparation method thereof modified based on bio-based polymers
CN109438653A (en) * 2018-10-26 2019-03-08 万华化学集团股份有限公司 A kind of bion thermoplastic polyurethane elastomer and preparation method thereof

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Application publication date: 20200512