CN111635499A - Epoxy modified polyurethane resin, system, preparation method and application thereof - Google Patents
Epoxy modified polyurethane resin, system, preparation method and application thereof Download PDFInfo
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- CN111635499A CN111635499A CN202010504936.3A CN202010504936A CN111635499A CN 111635499 A CN111635499 A CN 111635499A CN 202010504936 A CN202010504936 A CN 202010504936A CN 111635499 A CN111635499 A CN 111635499A
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/2845—Monohydroxy epoxy compounds
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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
- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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Abstract
The invention discloses an epoxy modified polyurethane resin system, which not only overcomes the defect that the traditional polyurethane resin is not moisture-resistant in the processes of storage, transportation and use, but also retains the excellent and wide performance of the polyurethane resin. The resin system is obtained by chemical reaction of polyol micromolecules and polyester (polyether) polyol macromolecules with polyisocyanate, glycidyl and the like. The epoxy resin can form a cured product with excellent performance with an amine curing agent and a sulfhydryl curing agent, and can be used for base resin systems of coatings, adhesives, composite materials, sealing (encapsulating) materials and the like with various performance requirements.
Description
Technical Field
The invention relates to a chemically synthesized resin, in particular to an epoxy modified polyurethane resin system, and a preparation method and application thereof.
Background
Polyurethane resin is a multifunctional resin material, which is widely applied to the fields of various buildings, textile clothing, petrochemical industry, transportation, electronic equipment, national defense water conservancy, medical sanitation and the like in the forms of foam, coating, elastomers, adhesives, flooring materials, artificial leather, waterproof materials and the like. However, the general thermosetting polyurethane resin molecule contains isocyanate group, and is easy to react with water vapor (i.e. moisture) to solidify, so that the general thermosetting polyurethane resin molecule causes inconvenience in storage, transportation and use, often causes waste and environmental pollution, and greatly limits the application range of the general thermosetting polyurethane resin molecule.
Disclosure of Invention
The invention aims to provide an epoxy modified polyurethane resin, a system, a preparation method and application thereof, aiming at overcoming the defect that the common thermosetting polyurethane resin is easy to react with water vapor and solidify when being used as a coating, an adhesive, a material and the like.
The technical scheme of the invention is to provide an epoxy modified polyurethane resin which is characterized in that the chemical structural formula is as follows:
wherein m is a natural number of 1 to 6;
r is a polyether polyol chain segment or a polyester polyol chain segment with the molecular weight of 100-2000;
r' is the core group of diisocyanate and the structure comprises:
the structure of M is related to the value of M if
When M is 1, then M is:
h-, 1-18C aliphatic group,
When M is 2, M is:
when M is 3, M is:
when M is 4, M is:
t is a nuclear group of epoxy alcohol, and the structure of the epoxy alcohol comprises:
The invention also provides an epoxy modified polyurethane resin system, which is characterized in that: the epoxy modified polyurethane resin comprises at least one epoxy modified polyurethane resin and a curing agent, wherein the curing agent is an amine curing agent and/or a sulfydryl curing agent; the epoxy modified polyurethane resin is cured at normal temperature or cured by heating through an amine curing agent and/or a sulfydryl curing agent.
Furthermore, the amine curing agent comprises aliphatic polyamine, alicyclic polyamine, aromatic polyamine, and various macromolecules and high-molecular polyamines derived from the micromolecular polyamine.
The invention also provides a preparation method of the epoxy modified polyurethane resin, which is characterized by comprising the following steps:
adding polyisocyanate, a polymerization inhibitor and a catalyst into a reaction container, uniformly stirring, heating, dropwise adding epoxy alcohol into the reaction container at the temperature of 45-65 ℃, heating to 75-105 ℃ for reflux after dropwise adding, and continuously stirring and reacting until the total isocyanuric value is reduced to a half of the initial value;
and step two, maintaining the temperature between 75 and 105 ℃ under stirring, dropwise adding the polyol, the polyether polyol and/or the polyester polyol into the mixture obtained in the step one, and continuing to react until the isocyanate value is reduced to 0, so that the reaction is finished.
Further, the ratio of the amount of the substance of the polyisocyanate to the amount of the substance of the epoxy alcohol is 1.10 to 1.00: 1.00.
Further, the polymerization inhibitor is acyl chloride and/or hydrochloric acid-phosphoric acid, and the mass percentage of the polymerization inhibitor in the total mass is 0.5-2.0%; the catalyst is organic tin, and the mass percentage of the catalyst in the total mass is 0.05-1.00%.
Further, the organic tin is dibutyltin dilaurate; the acyl chloride is benzoyl chloride.
The invention also provides another preparation method of the epoxy modified polyurethane resin, which is characterized by comprising the following steps: and (3) directly dripping epoxy alcohol into the isocyanate-terminated polyurethane prepolymer, and maintaining the temperature at 70-120 ℃ until the isocyanate value is 0.
Further, the ratio of the isocyanate value of the isocyanate-terminated polyurethane prepolymer to the hydroxyl value of the epoxy alcohol is 1.00 to 1.00: 1.30.
The invention also provides application of the epoxy modified polyurethane resin system in various coatings, adhesives, composite materials or sealing materials.
The invention has the beneficial effects that:
1. the invention carries out epoxy blocking modification on the isocyanate group of the general thermosetting polyurethane resin, so that the isocyanate group of the general thermosetting polyurethane resin can be cured in a mode of curing the epoxy resin, thereby not only solving the problem of moisture resistance of the polyurethane resin, but also keeping the inherent characteristics of the polyurethane resin.
2. The epoxy modified polyurethane resin system synthesized by the invention can be naturally cured or heated and baked and cured with amine curing agent and/or sulfydryl curing agent at normal temperature in any proportion.
3. The resin system formed by the epoxy modified polyurethane resin synthesized by the invention, the amine curing agent and the sulfydryl curing agent can be used for various coatings, adhesives, composite materials and sealing (encapsulating) materials.
Detailed Description
The epoxy modified polyurethane resin of the present invention can be represented by the following general formula:
wherein m is a natural number of 1 to 6;
r is a polyether polyol chain segment or a polyester polyol chain segment with the molecular weight of 100-2000;
r' is the core group of diisocyanate and the structure comprises:
the structure of M is related to the value of M if
When M is 1, M is:
h-, 1-18C aliphatic group,
When M is 2, M is:
when M is 3, M is:
when M is 4, M is:
t is a nuclear group of epoxy alcohol, and the structure of the epoxy alcohol comprises:
The epoxy modified polyurethane resin is prepared by the following two methods:
the first method is as follows:
step (1), adding all polyisocyanates (the amount of the polyisocyanate is 1.10-1.00: 1.00) into a three-necked bottle provided with a reflux condenser, a thermometer and a stirring device; adding a polymerization inhibitor (acyl chloride or hydrochloric acid-phosphoric acid or a mixture) accounting for 0.5-2.0% of the total mass and a catalyst (organic tin) accounting for 0.05-1.00%, stirring, dropwise adding epoxy alcohol at a temperature of 45-65 ℃, heating to 75-105 ℃ after dropwise adding, continuing stirring and reacting until the total isocyanic value is reduced to half of the initial value.
And (2) dripping the polyol and the polyether (or polyester) polyol independently or in a mixture of any proportion into the mixture in the step (1) under stirring at the temperature of 75-105 ℃ (the total isocyanate value: the total hydroxyl value is 1.00:1.00) until the isocyanate value is reduced to 0, and finishing the reaction.
The second method is as follows:
and (3) directly dripping epoxy alcohol into the isocyanate-terminated polyurethane prepolymer, and maintaining the temperature at 70-120 ℃ until the isocyanate value is 0. Wherein the ratio of the isocyanate value of the isocyanate-terminated polyurethane prepolymer to the hydroxyl value of the epoxy alcohol is 1.00 to 1.00: 1.30.
The reaction principle is as follows:
the above test method measures the isocyanate value according to GB/T120009.4-89 and monitors the characteristic absorption peak of isocyano group by red light spectrum.
The present invention is further described in detail in the following examples, which include but are not limited to the examples given:
example one
Placing the three-neck flask, reflux condenser tube, constant pressure dropping funnel and other instruments in a 120 ℃ oven for drying for 1.5h, taking out, placing in a dryer for cooling, installing, adding 0.16moL Toluene Diisocyanate (TDI), 0.1-0.5% (total weight) dibutyltin dilaurate (DBTDL) and 0.5-1.0% (total weight) benzoyl chloride into the three-neck flask, stirring uniformly, heating to 45 ℃, dropping 0.15moL glycidyl into the system by using the constant pressure dropping funnel, and dropping other epoxy alcohols such as epoxy alcohol in other embodiments
The ratio of the amount of polyisocyanate to the amount of epoxy alcohol is within the range of 1.10 to 1.00: 1.00. And then maintaining the temperature at 46-65 ℃. After the dropwise addition, the reaction was stopped after gradually increasing the temperature to 95 ℃ until the isocyanate value reached half of the total starting value. The temperature is reduced to 75 ℃, and 0.05moL of polyether 5000 is dripped. After the addition, the temperature is gradually increased to 10 DEGAnd continuing the reaction at 0 ℃, and stopping the reaction after the isocyanate value is reduced to be close to zero to obtain a light yellow transparent viscous liquid.
Example two
A condenser, a dropping funnel, a stirrer, a thermometer and the like were attached to the dried three-necked flask, and 0.16moL of Hexamethylene Diisocyanate (HDI), 0.1 to 0.5% by weight of dibutyltin dilaurate (DBTDL) and 0.5 to 1.0% by weight of a hydrochloric acid-phosphoric acid mixture were added to the three-necked flask. In other embodiments, 0.05 to 1.00 weight percent dibutyltin dilaurate (DBTDL) and 0.5 to 2.0 weight percent hydrochloric acid-phosphoric acid mixture may be added. After stirring, the temperature is raised to 55 ℃, 0.15moL of glycidol is added into the system by a constant pressure dropping funnel, and other epoxy alcohol, such as epoxy alcohol, can be added into the system
The ratio of the amount of polyisocyanate to the amount of epoxy alcohol is within the range of 1.10 to 1.00: 1.00. Maintaining the temperature at 46-65 ℃. After the dropwise addition, the temperature is gradually increased to 100 ℃ until the isocyanate value reaches half of the total initial value, and then the reaction is stopped. And cooling to 85 ℃, dropwise adding a mixture of 0.03moL of trifunctional polyether 3000 and 0.03moL of bifunctional polyether 2000, gradually heating to 105 ℃ after the addition is finished, continuing the reaction, and stopping the reaction after the isocyanate value is reduced to be close to zero to obtain a light yellow transparent viscous liquid.
EXAMPLE III
A condenser tube, a dropping funnel, a stirrer, a thermometer and other instruments are arranged on a dry three-neck flask, 0.16moL of Xylylene Diisocyanate (XDI), 0.1-0.5 percent (total weight) of dibutyltin dilaurate (DBTDL) and 0.5-1.0 percent (total weight) of hydrochloric acid-phosphoric acid mixture are added into the three-neck flask, the mixture is uniformly stirred and heated to 55 ℃, and 0.15moL of hydrochloric acid-phosphoric acid mixture is dripped into the system by using a constant-pressure dropping funnel
In other embodiments, other epoxy alcohols, such as glycidyl, can be added dropwise while maintaining the temperature at 46-65 ℃. After the dropwise adding, the temperature is gradually increased to 100 ℃ until isocyanic acidThe reaction was stopped after the value reached half of the total starting value. Cooling to 85 ℃, dropwise adding a mixture of 0.01moL of trimethylolpropane and 0.06moL of bifunctional polyester 2000, gradually heating to 105 ℃ after the addition, continuing the reaction, and stopping the reaction after the isocyanate value is reduced to be close to zero to obtain a light yellow transparent viscous liquid.
Example four
50 g of the epoxy-modified polyurethane resin synthesized in example one was uniformly mixed with 2.1 g of 2,2, 4-trimethyl-1, 6-hexanediamine, and the mixture was drawn on a glass plate to a thickness of about 2 mm. Surface-dried at room temperature (15-25 ℃) for 6 hours, and dried after 24 hours. The elongation at break is 465% and the breaking strength is 2.51 MPa. Can be used for coating, adhesive, composite material, sealing (encapsulating) material, etc.
EXAMPLE five
50 g of epoxy modified polyurethane resin synthesized in the third embodiment and 5.2 g of triethylene tetramine are uniformly mixed and blade-coated on two carbon steel plates, and the two carbon steel plates are overlapped by 2cm2. At room temperature (15-25 deg.C), 2kg/cm2The shear strength after 24 hours under load is 51.5MPa, and the material can be used for coatings, adhesives, composite materials, sealing (encapsulating) materials and the like.
Claims (10)
1. An epoxy modified polyurethane resin is characterized in that the chemical structural formula is as follows:
wherein m is a natural number from 1 to 6;
r is a polyether polyol chain segment or a polyester polyol chain segment with the molecular weight of 100-2000;
r' is the core group of diisocyanate and the structure comprises:
-(CH2)6-、
the structure of M is related to the value of M if
When M is 1, then M is:
h-, 1-18C aliphatic group,
When M is 2, M is:
-(CH2)2-、-(CH2)4-、-(CH2)6-、
when M is 3, M is:
when M is 4, M is:
t is a nuclear group of epoxy alcohol, and the structure of the epoxy alcohol comprises:
-(CH2)n-、-CH2(OCH2CH2)n-、
wherein n is a natural number from 1 to 6.
2. An epoxy modified polyurethane resin system, characterized in that: comprises at least one epoxy modified polyurethane resin as described in claim 1 and a curing agent, wherein the curing agent is an amine curing agent and/or a mercapto curing agent; the epoxy modified polyurethane resin is cured at normal temperature or cured by heating through an amine curing agent and/or a sulfydryl curing agent.
3. The epoxy-modified polyurethane resin system according to claim 2, wherein: the amine curing agent comprises aliphatic polyamine, alicyclic polyamine, aromatic polyamine, and various macromolecules and high-molecular polyamine derived from the micromolecular polyamine.
4. A method for preparing the epoxy modified polyurethane resin as claimed in claim 1, comprising the steps of:
adding polyisocyanate, a polymerization inhibitor and a catalyst into a reaction container, uniformly stirring, heating, dropwise adding epoxy alcohol into the reaction container at the temperature of 45-65 ℃, heating to 75-105 ℃ for reflux after dropwise adding, and continuously stirring and reacting until the total isocyanuric value is reduced to a half of the initial value;
and step two, maintaining the temperature between 75 and 105 ℃ under stirring, dropwise adding the polyol, the polyether polyol and/or the polyester polyol into the mixture obtained in the step one, and continuing to react until the isocyanate value is reduced to 0, so that the reaction is finished.
5. The method for producing an epoxy-modified polyurethane resin according to claim 4, characterized in that: the ratio of the amount of polyisocyanate to the amount of epoxy alcohol is 1.10 to 1.00: 1.00.
6. The method for producing an epoxy-modified polyurethane resin according to claim 5, characterized in that: the polymerization inhibitor is acyl chloride and/or hydrochloric acid-phosphoric acid, and the mass percentage of the polymerization inhibitor in the total mass is 0.5-2.0%; the catalyst is organic tin, and the mass percentage of the catalyst in the total mass is 0.05-1.00%.
7. The method for producing an epoxy-modified polyurethane resin according to claim 6, characterized in that: the organic tin is dibutyltin dilaurate; the acyl chloride is benzoyl chloride.
8. A method for preparing the epoxy modified polyurethane resin as described in claim 1, characterized in that: and (3) directly dripping epoxy alcohol into the isocyanate-terminated polyurethane prepolymer, and maintaining the temperature at 70-120 ℃ until the isocyanate value is 0.
9. The method for producing an epoxy-modified polyurethane resin according to claim 8, characterized in that: the ratio of the isocyanate value of the isocyanate-terminated polyurethane prepolymer to the hydroxyl value of the epoxy alcohol is 1.00 to 1.00: 1.30.
10. Use of the epoxy-modified polyurethane resin system of claim 2 or 3 in various types of coatings, adhesives, composites or sealants.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539188A (en) * | 2022-01-22 | 2022-05-27 | 巩义市泛锐熠辉复合材料有限公司 | Preparation method and application of polyurethane foam anti-aging agent |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63132931A (en) * | 1986-11-25 | 1988-06-04 | Toshiba Corp | Epoxy resin composition for sealing semiconductor |
| US20040068060A1 (en) * | 2002-10-04 | 2004-04-08 | Ohrbom Walter H. | Powder coatings containing oxirane groups beta to urethane or urea groups |
| US20050090636A1 (en) * | 2003-10-22 | 2005-04-28 | Degussa Ag | High-reactivity polyurethane powder coating compositions based on epoxy-terminated polyaddition compounds containing uretdione groups |
| US20100087567A1 (en) * | 2007-03-20 | 2010-04-08 | Sika Technology Ag | Epoxy group-terminated polymers, the compositions thereof and the use thereof as impact resistance modifiers |
| CN103601868A (en) * | 2013-11-13 | 2014-02-26 | 中国林业科学研究院林产化学工业研究所 | Method for preparing terminated epoxypolyurethane through grease dimer acids |
| US20140275341A1 (en) * | 2013-03-15 | 2014-09-18 | Lake Region Manufacturing, Inc. d/b/a Lake Region Medical | Oxirane (ethylene oxide) polyurethane coatings |
| CN105218778A (en) * | 2015-10-21 | 2016-01-06 | 中山大桥化工集团有限公司 | A kind of epoxy terminated waterborne polyurethane resin and preparation method thereof |
| CN106832185A (en) * | 2017-01-04 | 2017-06-13 | 上海华峰材料科技研究院（有限合伙） | Epoxy-capped polyurethane resin of use for synthetic leather large arch dam and preparation method thereof |
| CN108707414A (en) * | 2018-05-18 | 2018-10-26 | 安徽朗凯奇建材有限公司 | A kind of epoxy resin modification polyurethane water-proof paint and preparation method thereof |
-
2020
- 2020-06-05 CN CN202010504936.3A patent/CN111635499A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63132931A (en) * | 1986-11-25 | 1988-06-04 | Toshiba Corp | Epoxy resin composition for sealing semiconductor |
| US20040068060A1 (en) * | 2002-10-04 | 2004-04-08 | Ohrbom Walter H. | Powder coatings containing oxirane groups beta to urethane or urea groups |
| US20050090636A1 (en) * | 2003-10-22 | 2005-04-28 | Degussa Ag | High-reactivity polyurethane powder coating compositions based on epoxy-terminated polyaddition compounds containing uretdione groups |
| US20100087567A1 (en) * | 2007-03-20 | 2010-04-08 | Sika Technology Ag | Epoxy group-terminated polymers, the compositions thereof and the use thereof as impact resistance modifiers |
| US20140275341A1 (en) * | 2013-03-15 | 2014-09-18 | Lake Region Manufacturing, Inc. d/b/a Lake Region Medical | Oxirane (ethylene oxide) polyurethane coatings |
| CN103601868A (en) * | 2013-11-13 | 2014-02-26 | 中国林业科学研究院林产化学工业研究所 | Method for preparing terminated epoxypolyurethane through grease dimer acids |
| CN105218778A (en) * | 2015-10-21 | 2016-01-06 | 中山大桥化工集团有限公司 | A kind of epoxy terminated waterborne polyurethane resin and preparation method thereof |
| CN106832185A (en) * | 2017-01-04 | 2017-06-13 | 上海华峰材料科技研究院（有限合伙） | Epoxy-capped polyurethane resin of use for synthetic leather large arch dam and preparation method thereof |
| CN108707414A (en) * | 2018-05-18 | 2018-10-26 | 安徽朗凯奇建材有限公司 | A kind of epoxy resin modification polyurethane water-proof paint and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 姚微等: "缩水甘油封端聚氨酯的合成及其改性环氧树脂的粘合性能", 《青岛化工学院学报》 * |
| 邓小亮等: "端环氧基聚氨酯的合成及其改性环氧涂层的冲蚀磨损性能", 《塑料工业》 * |
| 陈庚等: "缩水甘油封端聚氨酯的合成及其增韧改性环氧树脂的研究", 《工程塑料应用》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539188A (en) * | 2022-01-22 | 2022-05-27 | 巩义市泛锐熠辉复合材料有限公司 | Preparation method and application of polyurethane foam anti-aging agent |
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