CN113956428A - Novel polyurethane material and preparation method thereof - Google Patents

Novel polyurethane material and preparation method thereof Download PDF

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Publication number
CN113956428A
CN113956428A CN202111262805.XA CN202111262805A CN113956428A CN 113956428 A CN113956428 A CN 113956428A CN 202111262805 A CN202111262805 A CN 202111262805A CN 113956428 A CN113956428 A CN 113956428A
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polyol
degradation product
polyurethane material
preparation
novel polyurethane
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侯相林
张宁
邓天昇
赵雨花
王军威
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

The invention belongs to the field of polyurethane material synthesis and preparation, and particularly relates to a novel polyurethane material and a preparation method thereof. The invention mainly solves the problems of high price of the polyol, complex synthesis process and the like in the existing polyurethane synthesis process. According to the invention, aromatic polyol which is a thermosetting resin degradation product, or aromatic polyol which is a thermosetting resin degradation product and an oligomer polyol compound are blended and dehydrated, mixed with an organic solvent and an isocyanate compound, uniformly mixed and poured into a mold for curing, so as to obtain the novel polyurethane resin material. The invention has the advantages of raw material derived from solid waste, simple synthetic method, economic reaction process and environmental protection.

Description

Novel polyurethane material and preparation method thereof
Technical Field
The invention belongs to the field of polyurethane material synthesis and preparation, and particularly relates to a novel polyurethane material and a preparation method thereof.
Background
Polyurethane refers to a polymer containing urethane groups in the molecular structure. The urethane is generally obtained by reacting polyisocyanate (including diisocyanate) and polyol (including dihydric alcohol), and organic polyisocyanate and oligomer polyol (such as polyether, polyester and the like) are two main raw materials for preparing polyurethane, usually account for more than 80% of the weight of polyurethane products, and are widely applied to the fields of foam plastics, elastomers, coatings, adhesives, waterproof materials and the like. The polyol in the polyurethane synthesis process is derived from fossil fuel, and the preparation process is complex in process and high in price.
The thermosetting resin material structure contains polyol fragments, but the thermosetting resin material is difficult to degrade and recycle, which causes resource waste. The current chemical degradation methods for thermosetting resin wastes mainly comprise hydrolysis, alcoholysis, aminolysis and the like. However, if the degradation product obtained by the chemical degradation method can not be reused, new waste is generated, which is not beneficial to the carbon cycle process. The method for recycling the waste thermosetting resin mainly comprises the steps of crushing the resin, blending the crushed resin with the resin to be used as a filler, or chemically breaking chemical bonds in the resin and then reacting the broken resin with an amine or anhydride curing agent to form a new thermosetting resin. However, a large amount of new raw materials are required to be added during the curing process, and therefore, the degradation products can only replace part of the raw materials to synthesize the epoxy resin. In summary, the existing utilization mode of the thermosetting resin degradation product has the problems of low added value of the degradation product, low utilization rate, narrow application range and the like.
Polyol compounds are often used in the synthesis of polyurethane, but no resin degradation products are used in the current synthesis research of polyurethane. The thermosetting resin degradation product is used for replacing a polyol component in the polyurethane synthesis process, so that the waste thermosetting resin is utilized in a high-value mode, the synthesis cost of polyurethane can be reduced, and the polyurethane has wide application value.
Disclosure of Invention
Aiming at the problems in the polyurethane synthesis process, the invention provides a method for preparing polyurethane by recycling the thermosetting resin degradation product, which is convenient, low in cost, high in additional value and wide in application range.
In order to realize the purpose, the invention is realized by the following technical scheme:
the invention provides a novel polyurethane material, which is a novel polyurethane material with an aromatic glycidyl ether structure and is obtained by partially or completely replacing an oligomer polyol component in a polyurethane synthesis process with a thermosetting resin degradation product, and can be used in the fields of coatings, adhesives, rigid polyurethane foams, soft polyurethane foams, elastomers and the like.
In another aspect of the present invention, a method for preparing a novel polyurethane material is provided, which comprises the following steps:
the novel polyurethane resin material is prepared by blending and dehydrating aromatic polyol which is a thermosetting resin degradation product, or aromatic polyol which is a thermosetting resin degradation product and an oligomer polyol compound, mixing the mixture with an organic solvent and an isocyanate compound, uniformly mixing the mixture, and pouring the mixture into a mold for curing. The thermosetting resin degradation product obtained by the selective bond breaking method is often polyhydroxy compound, can replace all or part of polyol in the polyurethane synthesis process, and reacts with isocyanate to prepare new polyurethane. Meanwhile, the waste thermosetting resin material can be reused, and the requirement of the current double-carbon target is met.
Further, the thermosetting resin is an anhydride-cured epoxy resin or an epoxy vinyl ester resin. Both resins contain aromatic glycerol ether segments.
Further, the aromatic polyol which is a degradation product of the thermosetting resin is a glycidyl ether compound containing a polyhydroxy structure, and comprises bisphenol A glycidyl ether, bisphenol F glycidyl ether or bisphenol S glycidyl ether. The glycidyl ether compound containing the polyhydroxy structure is obtained by degrading thermosetting resin in a hydrolysis, alcoholysis, aminolysis and other modes.
Further, the thermosetting resin degradation product aromatic polyol and the oligomer polyol compound are blended into a mixture of the degradation product of the glycidyl ether compound containing a polyhydroxy structure and one or more of polyester polyol and polyether polyol in any ratio. The aromatic polyol can be reacted with the isocyanate compound independently, or can be mixed with other oligomer polyol compounds in any ratio and then reacted with the isocyanate, wherein the oligomer polyol compound is one or a mixture of polyester polyol and polyether polyol. The polyester polyol is one or a mixture of a plurality of polyethylene glycol adipate, polybutylene glycol adipate, polyethylene glycol-propylene glycol adipate, polyethylene glycol-butylene glycol adipate, polyethylene glycol-neopentyl glycol adipate, poly epsilon-caprolactone diol, polyethylene glycol carbonate and polybutylene glycol carbonate according to any ratio. The polyether polyol is one or more of polyoxypropylene glycol, polyethylene glycol ether, polypropylene glycol ether, polytetramethylene ether glycol, polyoxyethylene glycol and polybutadiene polyol which are mixed according to any ratio.
Further, the dehydration condition is that the vacuum degree is 0.01-0.1 MPa, and the dehydration lasts for 2-12 h at the temperature of 80-140 ℃. Polyols require sufficient removal of water molecules prior to reaction, which can undergo side reactions with isocyanate groups.
Further, the organic solvent can simultaneously dissolve organic matters without active hydrogen of degradation products, namely aromatic polyol, oligomer polyol and isocyanate. The organic solvent can be one or more of acetone, tetrahydrofuran, butanone, ethyl acetate and 1, 4-dioxane. The solvent can dissolve degradation products of aromatic polyol, oligomer polyol compound and isocyanate at the same time.
Further, the isocyanate compound is one or a mixture of toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4' -methylene bis (cyclohexyl isocyanate) and m-tetramethylene xylene diisocyanate.
Further, the thermosetting resin degradation product aromatic polyol, or the thermosetting resin degradation product aromatic polyol and oligomer polyol compound blend has a molar ratio of hydroxyl groups to isocyanate groups of 1: 0.1 to 10. The isocyanate content is too low, and the polyurethane can not be cured and crosslinked; too high isocyanate content affects the properties of the new polyurethane materials.
Further, the curing time is 10 min-48 h, and the curing temperature is room temperature-80 ℃. The curing time is too short, and the polyurethane material has residual solvent and cannot be fully cured; the curing time is too long, resulting in time waste. The curing temperature is lower than room temperature, the reaction is difficult to occur, and the reaction rate is too fast to control when the curing temperature is higher than 80 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) the novel polyurethane material is synthesized by using the thermosetting resin degradation product, so that the polyurethane material is green and environment-friendly;
(2) the synthesis cost of the polyurethane is reduced, the product has wide application range and high added value;
(3) the new polyurethane material has simple synthesis process and excellent material performance.
Drawings
FIG. 1 is a diagram showing the mechanism of synthesis of the novel polyurethane of the present invention.
Detailed Description
The following examples are given in the detailed description and the specific operation on the premise of the technical solutions of the present invention, but do not limit the protection scope of the patent of the present invention, and all technical solutions obtained by using equivalent alternatives or equivalent variations should fall within the protection scope of the present invention.
Example 1
10g of bisphenol A glycidyl ether (with hydroxyl content of 0.102mol) which is a degradation product of anhydride curing epoxy resin is dehydrated for 8h at 100 ℃ under the vacuum degree of 0.02MPa, and then the dehydrated product is poured into a mold to be cured for 24h at room temperature after being fully mixed with butanone and 0.051mol hexamethylene diisocyanate, and finally the polyurethane resin material is obtained after curing. As shown in figure 1, the degradation product of thermosetting resin is aromatic polyol compound, and the hydroxyl group of the aromatic polyol compound reacts with isocyanate to generate an amine ester bond, so that a novel polyurethane material is formed. The tensile strength of the polyurethane obtained was 44 MPa.
Example 2
10g of bisphenol F glycidyl ether (with hydroxyl content of 0.102mol) which is a degradation product of anhydride curing epoxy resin is dehydrated for 2h at 140 ℃ under the vacuum degree of 0.1MPa, and then the dehydrated bisphenol F glycidyl ether is fully mixed with tetrahydrofuran and 0.51mol of p-phenylene diisocyanate, poured into a mold and cured for 10min at 80 ℃, and finally the polyurethane resin material is obtained after curing.
Example 3
10g of bisphenol S glycidyl ether (with hydroxyl content of 0.102mol) which is a degradation product of anhydride curing epoxy resin is dehydrated for 12h at 80 ℃ under the vacuum degree of 0.01MPa, and is poured into a mould to be cured for 48h at 30 ℃ after being fully mixed with acetone and 0.0051mol of toluene diisocyanate, so as to obtain the polyurethane resin material after curing.
Example 4
10g of epoxy vinyl ester resin degradation product bisphenol A glycidyl ether (hydroxyl content is 0.088mol) is mixed with polyethylene glycol adipate with the hydroxyl content of 0.1mol, the mixture is dehydrated for 6h at 120 ℃ under the vacuum degree of 0.03MPa, the dehydrated mixture is fully mixed with ethyl acetate and 0.094mol of isophorone diisocyanate, the mixture is poured into a mold and cured for 12h at 40 ℃, and the polyurethane resin material is obtained after curing.
Example 5
10g of epoxy vinyl ester resin degradation product bisphenol F glycidyl ether (the hydroxyl content is 0.102mol) and 0.2mol of poly (pentanediol carbonate) are mixed, dehydrated for 4h at 90 ℃ under the vacuum degree of 0.04MPa, fully mixed with 1, 4-dioxane and 0.3mol of m-tetramethylxylene diisocyanate, poured into a mold and cured for 30min at 50 ℃, and the polyurethane resin material is obtained after curing.
Example 6
10g of epoxy vinyl ester resin degradation product bisphenol A glycidyl ether (with hydroxyl content of 0.088mol) and polyethylene glycol ether with hydroxyl content of 0.6mol are blended, dehydrated for 4h at 100 ℃ under the vacuum degree of 0.05MPa, and are fully mixed with tetrahydrofuran and 1mol of 4, 4' -methylene bis (cyclohexyl isocyanate), and then poured into a mold to be cured for 18h at 60 ℃, and the polyurethane resin material is obtained after curing.
Example 7
10g of bisphenol A glycidyl ether (with hydroxyl content of 0.088mol) which is a degradation product of anhydride curing epoxy resin is mixed with polypropylene glycol ether with hydroxyl content of 0.6mol, dehydrated for 4h at 110 ℃ under the vacuum degree of 0.06MPa, and poured into a mold to be cured for 36h at 70 ℃ after being fully mixed with tetrahydrofuran and 0.8mol of diphenylmethane diisocyanate, and the polyurethane resin material is obtained after curing.
Example 8
10g of bisphenol F glycidyl ether (with hydroxyl content of 0.108mol) which is a degradation product of anhydride curing epoxy resin is mixed with polybutylene adipate with hydroxyl content of 0.3mol, the mixture is dehydrated for 2h at 140 ℃ under the vacuum degree of 0.07MPa, and after the mixture is fully mixed with acetone and 0.5mol of toluene diisocyanate, the mixture is poured into a mold to be cured for 45h at 75 ℃, and the polyurethane resin material is obtained after curing.
Example 9
10g of bisphenol S glycidyl ether (hydroxyl content is 0.088mol) which is a degradation product of anhydride curing epoxy resin is mixed with polyethylene glycol adipate-propylene glycol ester with the hydroxyl content of 0.4mol, the mixture is dehydrated for 3h at 130 ℃ under the vacuum degree of 0.08MPa, and after the mixture is fully mixed with butanone and 1mol of p-phenylene diisocyanate, the mixture is poured into a mold to be cured for 40h at room temperature, and the polyurethane resin material is obtained after curing.
Example 10
10g of bisphenol A glycidyl ether (with hydroxyl content of 0.084mol) which is a degradation product of anhydride curing epoxy resin is mixed with polyethylene glycol adipate-butanediol ester with hydroxyl content of 0.5mol, the mixture is dehydrated for 4 hours at 120 ℃ under the vacuum degree of 0.09MPa, and after the mixture is fully mixed with ethyl acetate and 1.5mol of hexamethylene diisocyanate, the mixture is poured into a mold to be cured for 35 hours at 65 ℃, and the polyurethane resin material is obtained after curing.
Example 11
10g of bisphenol F glycidyl ether (with hydroxyl content of 0.088mol) which is a degradation product of anhydride curing epoxy resin is mixed with polyhexamethylene adipate with hydroxyl content of 0.01mol, the mixture is dehydrated for 5h at 110 ℃ under the vacuum degree of 0.01MPa, and after being fully mixed with tetrahydrofuran and 0.008mol of p-phenylene diisocyanate, the mixture is poured into a mold to be cured for 30h at 55 ℃, and the polyurethane resin material is obtained after curing.
Example 12
10g of bisphenol S glycidyl ether (with hydroxyl content of 0.102mol) which is a degradation product of anhydride curing epoxy resin is mixed with 0.02mol of poly-glutaric adipate, dehydrated for 6h at 100 ℃ under the vacuum degree of 0.1MPa, and fully mixed with acetone and 0.3mol of 4, 4' -methylene bis (cyclohexyl isocyanate), poured into a mold to be cured for 25h at 45 ℃, and the polyurethane resin material is obtained after curing.
Example 13
10g of bisphenol A glycidyl ether (with hydroxyl content of 0.102mol) which is a degradation product of anhydride curing epoxy resin and polyethylene glycol adipate-neopentyl glycol with hydroxyl content of 0.03mol are blended, dehydrated for 7h at 90 ℃ under the vacuum degree of 0.06MPa, and are fully mixed with butanone and 0.4mol of m-tetramethylxylene diisocyanate, poured into a mold to be cured for 20h at room temperature, and the polyurethane resin material is obtained after curing.
Example 14
10g of epoxy vinyl ester resin degradation product bisphenol F glycidyl ether (with hydroxyl content of 0.088mol) and poly epsilon-caprolactone diol with hydroxyl content of 0.04mol are blended, dehydrated for 8h at 80 ℃ under the vacuum degree of 0.02MPa, and are fully mixed with ethyl acetate and 0.0094mol of isophorone diisocyanate, poured into a mold and cured for 15h at 35 ℃, and the polyurethane resin material is obtained after curing.
Example 15
10g of bisphenol S glycidyl ether (hydroxyl content is 0.084mol) which is a degradation product of epoxy vinyl ester resin is mixed with 0.05mol of poly (hexamethylene carbonate), the mixture is dehydrated for 9h at 140 ℃ under the vacuum degree of 0.03MPa, tetrahydrofuran and 0.01mol of p-phenylene diisocyanate are added into the mixture to be fully mixed, the mixture is poured into a mold to be cured for 10h at 25 ℃, and the polyurethane resin material is obtained after curing.
Example 16
10g of epoxy vinyl ester resin degradation product bisphenol A glycidyl ether (with hydroxyl content of 0.102mol) and 0.06mol of polycarbonate butanediol ester are blended, dehydrated for 10h at 130 ℃ under the vacuum degree of 0.03MPa, and are fully mixed with acetone and 0.08mol of m-tetramethylxylene diisocyanate, and then poured into a mold to be cured for 5h at room temperature, and the polyurethane resin material is obtained after curing.
Example 17
10g of epoxy vinyl ester resin degradation product bisphenol A glycidyl ether (hydroxyl content is 0.104mol) and polyoxypropylene glycol with the hydroxyl content of 0.07mol are blended, dehydrated for 11h at 120 ℃ under the vacuum degree of 0.04MPa, poured into a mold to be cured for 1h at 30 ℃ after being fully mixed with butanone and 0.4mol of isophorone diisocyanate, and the polyurethane resin material is obtained after curing.
Example 18
10g of epoxy vinyl ester resin degradation product bisphenol F glycidyl ether (with hydroxyl content of 0.088mol) and polytetramethylene ether glycol with hydroxyl content of 0.08mol are blended, dehydrated for 12h at 115 ℃ under the vacuum degree of 0.05MPa, and are fully mixed with ethyl acetate and 0.7mol of hexamethylene diisocyanate, poured into a mold and cured for 30min at 40 ℃ to obtain the polyurethane resin material after curing.
Example 19
10g of bisphenol S glycidyl ether (hydroxyl content is 0.082mol) which is a degradation product of epoxy vinyl ester resin is mixed with polyoxyethylene glycol with the hydroxyl content of 0.09mol, dehydrated for 6.5h at 125 ℃ under the vacuum degree of 0.06MPa, and fully mixed with tetrahydrofuran and 0.05mol of 4, 4' -methylene bis (cyclohexyl isocyanate), poured into a mold and cured for 50min at 50 ℃, and the polyurethane resin material is obtained after curing.
Example 20
10g of epoxy vinyl ester resin degradation product bisphenol A glycidyl ether (hydroxyl content is 0.088mol) and polybutadiene polyol with the hydroxyl content of 0.1mol are blended, dehydrated for 3.5h at 135 ℃ under the vacuum degree of 0.07MPa, fully mixed with ethyl acetate and 0.094mol of isophorone diisocyanate, poured into a mold and cured for 12h at room temperature, and the polyurethane resin material is obtained after curing.

Claims (10)

1. A novel polyurethane material is characterized in that: the novel polyurethane material is a novel polyurethane material with an aromatic glycidyl ether structure, which is obtained by partially or completely replacing an oligomer polyol component in the polyurethane synthesis process with a thermosetting resin degradation product.
2. A preparation method of a novel polyurethane material is characterized by comprising the following steps: the method comprises the following steps:
the novel polyurethane resin material is prepared by blending and dehydrating aromatic polyol which is a thermosetting resin degradation product, or aromatic polyol which is a thermosetting resin degradation product and an oligomer polyol compound, mixing the mixture with an organic solvent and an isocyanate compound, uniformly mixing the mixture, and pouring the mixture into a mold for curing.
3. A process for the preparation of a novel polyurethane material according to claim 2, characterized in that: the thermosetting resin is anhydride cured epoxy resin or epoxy vinyl ester resin.
4. A process for the preparation of a novel polyurethane material according to claim 2, characterized in that: the aromatic polyol which is a degradation product of the thermosetting resin is a glycidyl ether compound containing a polyhydroxy structure, and comprises bisphenol A glycidyl ether, bisphenol F glycidyl ether or bisphenol S glycidyl ether; the thermosetting resin degradation product aromatic polyol and oligomer polyol compound are blended into a mixture of the degradation product of the glycidyl ether compound with a polyhydroxy structure and one or more of polyester polyol and polyether polyol in any ratio.
5. A process for the preparation of a novel polyurethane material according to claim 4, characterized in that: the polyester polyol is one or more of polyethylene glycol adipate, polybutylene glycol adipate, polyethylene glycol-propylene glycol adipate, polyethylene glycol-butylene glycol adipate, polyethylene glycol adipate, polybutylene glycol adipate, polyethylene glycol-neopentyl glycol adipate, poly epsilon-caprolactone diol, polyhexamethylene glycol carbonate, polybutylene glycol carbonate and polybutylene glycol carbonate which are mixed according to any ratio; the polyether polyol is one or a mixture of more of polyoxypropylene glycol, polyethylene glycol ether, polypropylene glycol ether, polytetramethylene ether glycol, polyoxyethylene glycol and polybutadiene polyol according to any ratio.
6. A process for the preparation of a novel polyurethane material according to claim 2, characterized in that: the dehydration condition is that the vacuum degree is 0.01-0.1 MPa, and the dehydration lasts for 2-12 h at the temperature of 80-140 ℃.
7. A process for the preparation of a novel polyurethane material according to claim 2, characterized in that: the organic solvent is organic matter which can dissolve degradation products of aromatic polyol, oligomer polyol and isocyanate and does not contain active hydrogen.
8. A process for the preparation of a novel polyurethane material according to claim 7, characterised in that: the organic solvent is one or a mixture of acetone, tetrahydrofuran, butanone, ethyl acetate and 1, 4-dioxane.
9. A process for the preparation of a novel polyurethane material according to claim 2, characterized in that: the isocyanate compound is one or a mixture of toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4' -methylene bis (cyclohexyl isocyanate) and m-tetramethylene xylene diisocyanate.
10. A process for the preparation of a novel polyurethane material according to claim 2, characterized in that: the molar ratio of hydroxyl groups to isocyanate groups in the thermosetting resin degradation product aromatic polyol or the thermosetting resin degradation product aromatic polyol and oligomer polyol compound blend is 1: 0.1 to 10; the curing time is 10 min-48 h, and the curing temperature is room temperature-80 ℃.
CN202111262805.XA 2021-10-28 2021-10-28 Novel polyurethane material and preparation method thereof Pending CN113956428A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54106456A (en) * 1978-02-08 1979-08-21 Mitsubishi Petrochem Co Ltd Novel hydroxyalkylation process of bisphenols
PL244425A2 (en) * 1983-11-04 1984-09-10 Politechnika Warszawska Process for manufacturing polyfunctional polyols
CN110157038A (en) * 2019-04-11 2019-08-23 四川大学 A method of the low temperature fast degradation of the macromolecule resin containing ester bond and separation
CN111333814A (en) * 2020-04-10 2020-06-26 万华化学集团股份有限公司 Thermoplastic polyurethane, preparation method and application thereof
CN111718515A (en) * 2020-07-08 2020-09-29 中国科学院山西煤炭化学研究所 Method for degrading epoxy resin cured by catalytic anhydride

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54106456A (en) * 1978-02-08 1979-08-21 Mitsubishi Petrochem Co Ltd Novel hydroxyalkylation process of bisphenols
PL244425A2 (en) * 1983-11-04 1984-09-10 Politechnika Warszawska Process for manufacturing polyfunctional polyols
CN110157038A (en) * 2019-04-11 2019-08-23 四川大学 A method of the low temperature fast degradation of the macromolecule resin containing ester bond and separation
CN111333814A (en) * 2020-04-10 2020-06-26 万华化学集团股份有限公司 Thermoplastic polyurethane, preparation method and application thereof
CN111718515A (en) * 2020-07-08 2020-09-29 中国科学院山西煤炭化学研究所 Method for degrading epoxy resin cured by catalytic anhydride

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