Environment-friendly PU (polyurethane) resin and preparation process thereof

Abstract

The invention relates to a preparation process of environment-friendly PU (polyurethane) resin. Comprising the following steps: a primary polymerization reaction step, a secondary polymerization reaction step, a primary chain extension reaction step, a secondary chain extension reaction step and a dilution step: adding 80-100 parts by mass of water, 30-60 parts by mass of a diluent, 1000-1200 parts by mass of a solvent and 20-40 parts by mass of an emulsifier into a reaction kettle, and uniformly mixing and stirring, the heating temperature of the reaction kettle is 50-60 DEG C, and the heating time is 10-20 minutes. A blending step: adding 40-100 parts by mass of a high-temperature-resistant filler, 10-20 parts by mass of an anti-aging agent, 30-60 parts by mass of a toughening agent, 5-10 parts by mass of a defoaming agent and 15-25 parts by mass of a coupling agent into the reaction kettle, and uniformly mixing and stirring to obtain environment-friendly PU resin; the heating temperature of the reaction kettle is 50-60 DEG C, and the heating time is 10-20 minutes.

Description

Technical Field

[0001] The present invention relates to the field of resin glue, in particular to an environmentally friendly PU resin and a preparation process thereof. Background Art

[0002] Polyurethane, or polyurethane, is a polymer material formed by the polycondensation reaction of polyols and polyisocyanates. It exhibits excellent mechanical properties and exceptional plasticity. With technological advancements, polyurethane has expanded its applications to include coatings, adhesives, fabric finishes, leather modifiers, flexible and rigid polyurethane foams, and elastomers. Applications include textiles, construction, aviation, shipbuilding, transportation, medicine, and electronics. Soft polyurethane, primarily a thermoplastic linear structure, offers superior stability, chemical resistance, resilience, and mechanical properties compared to PVC foam, with minimal compression deformation. It also exhibits excellent thermal, sound, shock, and toxic properties. Therefore, it is used in packaging, sound insulation, and filter materials. Rigid polyurethane plastics are lightweight, offer superior sound and thermal insulation properties, are chemically resistant, have excellent electrical properties, are easy to process, and have low water absorption. Rigid polyurethane plastics are primarily used as structural materials in construction, the automotive and aviation industries, and for thermal insulation. Polyurethane elastomers possess properties intermediate between those of plastics and rubber, including oil resistance, wear resistance, low-temperature resistance, aging resistance, high hardness, and elasticity.

[0003] However, traditional polyurethane resins, such as the technical solution to be protected in the patent application number CN201080033151.7, entitled "Aqueous Polyurethane Resin Dispersion and Method for Making the Same," have poor high temperature resistance and low thermal stability. Summary of the Invention

[0004] Based on this, it is necessary to provide an environmentally friendly PU resin preparation process to address the technical problems of poor high temperature resistance and low thermal stability of traditional polyurethane resins.

[0005] A process for preparing an environmentally friendly PU resin comprises the following steps: The primary polymerization reaction step comprises adding 130 to 170 parts by weight of a diol and 50 to 70 parts by weight of an isocyanate to a reactor, mixing and stirring the mixture uniformly, and then performing a heating polymerization reaction; the heating temperature is 60 to 80 degrees Celsius, and the heating time is 2 to 3 hours; Secondary polymerization reaction step: adding 30 to 60 parts by weight of polyol to the above-mentioned reactor, mixing and stirring uniformly to carry out heating polymerization reaction; heating temperature is 80 degrees Celsius to 100 degrees Celsius, and time is 3 hours to 4 hours; Initial chain extension reaction step: adding 10 to 18 parts by weight of the first chain extender and 1 to 2 parts by weight of the catalyst to the above-mentioned reactor, mixing and stirring uniformly to carry out a heating chain extension reaction; heating temperature is 70 degrees Celsius to 80 degrees Celsius, and time is 2.5 hours to 3.5 hours; Second chain extension reaction step: adding 12 to 20 parts by weight of the second chain extender to the above reactor, mixing and stirring uniformly to carry out heating chain extension reaction; heating temperature is 80 degrees Celsius to 90 degrees Celsius, and time is 3 hours to 4.5 hours; Dilution step: add 80 to 100 parts by weight of water, 30 to 60 parts by weight of diluent, 1000 to 1200 parts by weight of solvent, and 20 to 40 parts by weight of emulsifier to the above-mentioned reactor and mix and stir evenly. The reactor is heated at a temperature of 50 to 60 degrees Celsius for 10 to 20 minutes. Modulation step: adding 40 to 100 parts by weight of a high-temperature resistant filler, 10 to 20 parts by weight of an antioxidant, 30 to 60 parts by weight of a toughening agent, 5 to 10 parts by weight of a defoaming agent, and 15 to 25 parts by weight of a coupling agent to the above-mentioned reactor and mixing and stirring evenly to obtain an environmentally friendly PU resin; the reactor is heated to a temperature of 50 to 60 degrees Celsius for 10 to 20 minutes.

[0006] In one embodiment, in the primary polymerization reaction step, the diol includes the following components in parts by weight: 20 to 30 parts of polytetramethyl ether glycol, 10 to 25 parts of polycaprolactone diol, 15 to 35 parts of polycarbonate diol, 10 to 20 parts of polytetramethylene ether glycol, and 14 to 26 parts of polypropylene glycol.

[0007] In one embodiment, in the primary polymerization reaction step, the isocyanate includes the following components in parts by weight: 14 to 24 parts of isophorone diisocyanate, 16 to 26 parts of hexamethylene diisocyanate, 25 to 35 parts of dicyclohexylmethane diisocyanate, 15 to 25 parts of toluene diisocyanate, and 18 to 26 parts of xylylene diisocyanate.

[0008] In one embodiment, in the repolymerization step, the polyol includes the following components in parts by weight: 23 to 33 parts of polytetramethylene ether polyol, 17 to 27 parts of polyethylene oxide polyol, 24 to 36 parts of polypropylene oxide polyol, and 14 to 26 parts of polysiloxane polyol.

[0009] In one embodiment, in the initial chain extension reaction step, the first chain extender includes the following components in parts by weight: 12 to 22 parts of butanediol, 8 to 12 parts of ethylene glycol, 8 to 22 parts of diethylene glycol, 13 to 24 parts of propylene glycol, 7 to 14 parts of glucitol, 16 to 32 parts of mannitol, and 11 to 23 parts of pentaerythritol.

[0010] In one embodiment, in the second chain extension reaction step, the second chain extender includes the following components in parts by weight: 11 to 21 parts of ethylenediamine, 13 to 18 parts of isophoronediamine, 15 to 28 parts of diethylenetriamine, 14 to 27 parts of dimethylolpropionic acid, 13 to 25 parts of dimethylolbutyric acid, and 7 to 14 parts of trimethylolpropane.

[0011] In one embodiment, in the initial chain extension reaction step, the catalyst is stannous octoate.

[0012] In one embodiment, in the dilution step, the diluent is polyvinyl alcohol.

[0013] In one embodiment, in the dilution step, the solvent is a mixture of dimethylformamide and ethyl acetate.

[0014] An environmentally friendly PU resin is prepared by the environmentally friendly PU resin preparation process described in any of the above embodiments.

[0015] The environmentally friendly PU resin preparation process is simple, sophisticated, and easy to operate. The environmentally friendly PU resin obtained by the environmentally friendly PU resin preparation process has excellent high temperature resistance, high thermal stability, and excellent antioxidant properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 Flowchart of a process for preparing an environmentally friendly PU resin in one embodiment. DETAILED DESCRIPTION

[0017] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below with reference to the accompanying drawings. In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below. In the description of the present invention, it should be understood that the orientation or position relationship indicated by the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential" etc. is based on the orientation or position relationship shown in the accompanying drawings, and is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the present invention.

[0018] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of the technical features being referred to. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "plurality" means at least two, such as two, three, etc., unless otherwise specifically defined.

[0019] In the present invention, unless otherwise specified or limited, the terms "installed," "connected," "connect," "fixed," etc. should be understood in a broad sense. For example, they can refer to fixed connection, detachable connection, or integration; mechanical connection, electrical connection; direct connection, or indirect connection through an intermediate medium; internal communication between two components, or interaction between two components, unless otherwise specified. Those skilled in the art will understand the specific meanings of the above terms in the present invention based on specific circumstances.

[0020] In the present invention, unless otherwise expressly specified or limited, when a first feature is "above" or "below" a second feature, it may mean that the first and second features are in direct contact, or that the first and second features are in indirect contact through an intermediary. Furthermore, when a first feature is "above," "above," or "above" a second feature, it may mean that the first feature is directly above or diagonally above the second feature, or simply means that the first feature is at a higher level than the second feature. When a first feature is "below," "below," or "below" a second feature, it may mean that the first feature is directly below or diagonally below the second feature, or simply means that the first feature is at a lower level than the second feature.

[0021] It should be noted that when an element is referred to as being "fixed to" or "disposed on" another element, it may be directly on the other element or there may be an intermediate element. When an element is considered to be "connected to" another element, it may be directly connected to the other element or there may be an intermediate element. The terms "vertical," "horizontal," "upper," "lower," "left," "right," and similar expressions used herein are for illustrative purposes only and do not represent the only implementation methods.

[0022] See also Figure 1 The present invention provides an environmentally friendly PU resin preparation process, comprising the following steps: Step 101: Primary Polymerization: 130 to 170 parts by weight of diol and 50 to 70 parts by weight of isocyanate are added to a reactor, mixed and stirred uniformly, and then heated for polymerization. The heating temperature is 60 to 80 degrees Celsius for 2 to 3 hours.

[0023] In one embodiment, the diol comprises the following components in parts by weight: 20 to 30 parts of polytetramethyl ether glycol, 10 to 25 parts of polycaprolactone diol, 15 to 35 parts of polycarbonate diol, 10 to 20 parts of polytetramethylene ether diol, and 14 to 26 parts of polypropylene glycol. In one embodiment, the isocyanate comprises the following components in parts by weight: 14 to 24 parts of isophorone diisocyanate, 16 to 26 parts of hexamethylene diisocyanate, 25 to 35 parts of dicyclohexylmethane diisocyanate, 15 to 25 parts of toluene diisocyanate, and 18 to 26 parts of xylylene diisocyanate.

[0024] Specifically, 150 parts by weight of diol and 60 parts by weight of isocyanate were added to a reaction kettle, mixed and stirred uniformly, and then heated for polymerization reaction at a temperature of 75 degrees Celsius for 2.5 hours.

[0025] Step 102: Polymerization Reaction Step: 30 to 60 parts by weight of polyol are added to the above reactor, mixed and stirred uniformly, and then heated for polymerization reaction at a temperature of 80 to 100 degrees Celsius for 3 to 4 hours.

[0026] In one embodiment, the polyol includes the following components in parts by mass: 23 to 33 parts of polytetramethylene ether polyol, 17 to 27 parts of polyethylene oxide polyol, 24 to 36 parts of polypropylene oxide polyol and 14 to 26 parts of polysiloxane polyol.

[0027] Specifically, 50 parts by weight of polyol was added to the reactor, mixed and stirred evenly, and then heated for polymerization reaction at 90 degrees Celsius for 3.5 hours.

[0028] Step 103: Primary Chain Extension Reaction: 10 to 18 parts by weight of the first chain extender and 1 to 2 parts by weight of the catalyst are added to the reactor, mixed and stirred, and then heated for a chain extension reaction. The heating temperature is 70 to 80 degrees Celsius for 2.5 to 3.5 hours.

[0029] The catalyst is stannous octoate. The first chain extender comprises the following components in parts by weight: 12 to 22 parts of butanediol, 8 to 12 parts of ethylene glycol, 8 to 22 parts of diethylene glycol, 13 to 24 parts of propylene glycol, 7 to 14 parts of glucitol, 16 to 32 parts of mannitol, and 11 to 23 parts of pentaerythritol.

[0030] Specifically, 14 parts by weight of the first chain extender and 1.5 parts by weight of the catalyst were added to the reactor, mixed and stirred evenly, and then heated to perform a chain extension reaction at a temperature of 75 degrees Celsius for 3 hours.

[0031] Step 104: Second chain extension reaction: 12 to 20 parts by weight of the second chain extender are added to the reactor, mixed and stirred evenly, and then heated for chain extension reaction at a temperature of 80 to 90 degrees Celsius for 3 to 4.5 hours.

[0032] In one embodiment, the second chain extender includes the following components in parts by weight: 11 to 21 parts of ethylenediamine, 13 to 18 parts of isophoronediamine, 15 to 28 parts of diethylenetriamine, 14 to 27 parts of dimethylolpropionic acid, 13 to 25 parts of dimethylolbutanoic acid, and 7 to 14 parts of trimethylolpropane.

[0033] Specifically, 15 parts by weight of the second chain extender was added to the above reactor and mixed and stirred evenly to perform a heating chain extension reaction. The heating temperature was 85 degrees Celsius and the time was 3.5 hours. Step 105: Dilution step: add 80 to 100 parts by mass of water, 30 to 60 parts by mass of diluent, 1000 to 1200 parts by mass of solvent, and 20 to 40 parts by mass of emulsifier to the above-mentioned reactor and mix and stir evenly. The reactor is heated to a temperature of 50 to 60 degrees Celsius for 10 to 20 minutes.

[0034] Wherein, the diluent is polyvinyl alcohol and the solvent is a mixture of dimethylformamide and ethyl acetate.

[0035] Specifically, 90 parts by mass of water, 50 parts by mass of diluent, 1100 parts by mass of solvent, and 30 parts by mass of emulsifier were added to the above-mentioned reactor and mixed and stirred evenly. The reactor was heated at a temperature of 55 degrees Celsius for 15 minutes.

[0036] Step 106: Preparation: 40 to 100 parts by weight of a high-temperature resistant filler, 10 to 20 parts by weight of an antioxidant, 30 to 60 parts by weight of a toughening agent, 5 to 10 parts by weight of a defoaming agent, and 15 to 25 parts by weight of a coupling agent are added to the above-mentioned reactor and mixed and stirred to obtain an environmentally friendly PU resin. The reactor is heated to a temperature of 50 to 60 degrees Celsius for 10 to 20 minutes.

[0037] Specifically, 80 parts by weight of a high-temperature resistant filler, 15 parts by weight of an antioxidant, 50 parts by weight of a toughening agent, 8 parts by weight of a defoaming agent, and 20 parts by weight of a coupling agent were added to the above-mentioned reactor and mixed and stirred uniformly to obtain an environmentally friendly PU resin. The reactor was heated to 55 degrees Celsius for 15 minutes.

[0038] The present invention also provides an environmentally friendly PU resin, which is prepared by the environmentally friendly PU resin preparation process described in any of the above embodiments.

[0039] The environmentally friendly PU resin preparation process is simple, sophisticated, and easy to operate. The environmentally friendly PU resin obtained by the environmentally friendly PU resin preparation process has excellent high temperature resistance, high thermal stability, and excellent antioxidant properties.

[0040] To reduce bubbles in environmentally friendly PU resin, the defoamer includes the following components by weight: 20 to 40 parts dimethyl silicone oil, 25 to 45 parts polyoxypropylene glycerol ether, and 15 to 25 parts hydroxy polydimethylsiloxane. This defoamer can reduce bubbles in environmentally friendly PU resin.

[0041] To increase the flexibility of the environmentally friendly PU resin, the toughening agent includes the following components by weight: 30 to 60 parts of nitrile rubber, 15 to 30 parts of natural rubber latex, and 10 to 35 parts of latex powder. The toughening agent composed of the above components can increase the flexibility of the environmentally friendly PU resin.

[0042] To enhance the stability of the connections between the components within the environmentally friendly PU resin, the coupling agent includes the following components by weight: 10 to 20 parts methyltrimethoxysilane, 25 to 35 parts trimethylolpropane, 5 to 15 parts vinyltrimethoxysilane, 10 to 25 parts ethyl orthosilicate, and 15 to 30 parts vinyltriethoxysilane. This coupling agent enhances the stability of the connections between the components within the environmentally friendly PU resin, thereby increasing the stability of the resin.

[0043] To enhance the heat resistance of the environmentally friendly PU resin, the heat-resistant filler comprises the following components by weight: 10 to 20 parts silicone powder, 15 to 25 parts nano-alumina powder, 12 to 24 parts microsilica powder, 8 to 26 parts kaolin, 11 to 30 parts mica powder, 6 to 12 parts nano-titanium dioxide, and 14 to 20 parts bamboo charcoal powder. This heat-resistant filler enhances the heat resistance of the environmentally friendly PU resin.

[0044] To enhance the aging resistance of environmentally friendly PU resin, the antioxidant includes the following components by weight: 5 to 10 parts sodium oxalate, 5 to 10 parts calcium oxalate, 10 to 30 parts acetic acid hydrazide, 20 to 40 parts benzenesulfonyl hydrazide, and 10 to 30 parts antioxidant. Furthermore, the antioxidant is 2,6-di-tert-butyl-4-methylphenol. This antioxidant, composed of the above components, can enhance the aging resistance of environmentally friendly PU resin.

[0045] 1000 portions of the environmentally friendly PU resin were cured and cut into test blocks (100mm×10mm×4mm) for performance testing. The average test results are as follows:

[0046] The above test results show that the above high temperature resistant resin glue has excellent high temperature resistance, strong anti-aging performance, high structural strength after curing, excellent adhesion and strong flame retardant performance.

[0047] The technical features of the above embodiments can be combined arbitrarily. To make the description concise, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0048] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A process for preparing an environmentally friendly PU resin, characterized in that: The steps include: The primary polymerization reaction step comprises adding 130 to 170 parts by weight of a diol and 50 to 70 parts by weight of an isocyanate to a reactor, mixing and stirring the mixture uniformly, and then performing a heating polymerization reaction; the heating temperature is 60 to 80 degrees Celsius, and the heating time is 2 to 3 hours; Secondary polymerization reaction step: adding 30 to 60 parts by weight of polyol to the above-mentioned reactor, mixing and stirring uniformly to carry out heating polymerization reaction; heating temperature is 80 degrees Celsius to 100 degrees Celsius, and time is 3 hours to 4 hours; Initial chain extension reaction step: adding 10 to 18 parts by weight of the first chain extender and 1 to 2 parts by weight of the catalyst to the above-mentioned reactor, mixing and stirring uniformly to carry out a heating chain extension reaction; heating temperature is 70 degrees Celsius to 80 degrees Celsius, and time is 2.5 hours to 3.5 hours; Second chain extension reaction step: adding 12 to 20 parts by weight of the second chain extender to the above reactor, mixing and stirring uniformly to carry out heating chain extension reaction; heating temperature is 80 degrees Celsius to 90 degrees Celsius, and time is 3 hours to 4.5 hours; Dilution step: add 80 to 100 parts by weight of water, 30 to 60 parts by weight of diluent, 1000 to 1200 parts by weight of solvent, and 20 to 40 parts by weight of emulsifier to the above-mentioned reactor and mix and stir evenly. The reactor is heated at a temperature of 50 to 60 degrees Celsius for 10 to 20 minutes. Modulation step: adding 40 to 100 parts by weight of a high-temperature resistant filler, 10 to 20 parts by weight of an antioxidant, 30 to 60 parts by weight of a toughening agent, 5 to 10 parts by weight of a defoaming agent, and 15 to 25 parts by weight of a coupling agent to the above-mentioned reactor and mixing and stirring evenly to obtain an environmentally friendly PU resin; the reactor is heated to a temperature of 50 to 60 degrees Celsius for 10 to 20 minutes.

2. The process for preparing the environmentally friendly PU resin according to claim 1, wherein: In the primary polymerization step, the diol includes the following components in parts by mass: 20 to 30 parts of polytetramethyl ether glycol, 10 to 25 parts of polycaprolactone diol, 15 to 35 parts of polycarbonate diol, 10 to 20 parts of polytetramethylene ether glycol, and 14 to 26 parts of polypropylene glycol.

3. The process for preparing the environmentally friendly PU resin according to claim 1, wherein: In the primary polymerization step, the isocyanate includes the following components in parts by mass: 14 to 24 parts of isophorone diisocyanate, 16 to 26 parts of hexamethylene diisocyanate, 25 to 35 parts of dicyclohexylmethane diisocyanate, 15 to 25 parts of toluene diisocyanate, and 18 to 26 parts of xylylene diisocyanate.

4. The process for preparing the environmentally friendly PU resin according to claim 1, wherein: In the repolymerization step, the polyol includes the following components in parts by mass: 23 to 33 parts of polytetramethylene ether polyol, 17 to 27 parts of polyethylene oxide polyol, 24 to 36 parts of polypropylene oxide polyol, and 14 to 26 parts of polysiloxane polyol.

5. The process for preparing the environmentally friendly PU resin according to claim 1, characterized in that: In the primary chain extension reaction step, the first chain extender includes the following components in parts by mass: 12 to 22 parts of butanediol, 8 to 12 parts of ethylene glycol, 8 to 22 parts of diethylene glycol, 13 to 24 parts of propylene glycol, 7 to 14 parts of glucitol, 16 to 32 parts of mannitol, and 11 to 23 parts of pentaerythritol.

6. The process for preparing the environmentally friendly PU resin according to claim 1, characterized in that: In the second chain extension reaction step, the second chain extender includes the following components in parts by mass: 11 to 21 parts of ethylenediamine, 13 to 18 parts of isophoronediamine, 15 to 28 parts of diethylenetriamine, 14 to 27 parts of dimethylolpropionic acid, 13 to 25 parts of dimethylolbutanoic acid, and 7 to 14 parts of trimethylolpropane.

7. The process for preparing the environmentally friendly PU resin according to claim 1, characterized in that: In the primary chain extension reaction step, the catalyst is stannous octoate.

8. The process for preparing the environmentally friendly PU resin according to claim 1, wherein: In the dilution step, the diluent is polyvinyl alcohol.

9. The process for preparing the environmentally friendly PU resin according to claim 1, wherein: In the dilution step, the solvent is a mixture of dimethylformamide and ethyl acetate.

10. An environmentally friendly PU resin, characterized in that: The environmentally friendly PU resin is prepared by the preparation process of any one of claims 1 to 9.

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