Epoxy resin modified polyurethane foam plugging material and preparation method thereof

Abstract

The invention relates to the technical field of polyurethane materials, and proposes an epoxy resin modified polyurethane foam plugging material and a preparation method thereof. The epoxy resin modified polyurethane foam plugging material comprises component A and component B, wherein component A comprises the following component raw materials in parts by weight: 70-90 parts of polyether polyol, 10-30 parts of epoxy resin modified polyol, 2-4 parts of foaming agent, 0.5-1.5 parts of catalyst A, 0.5-1.5 parts of surfactant, and 8-10 parts of auxiliary agent, and component B is polymethylene polyphenyl polyisocyanate, and the epoxy resin in the raw material of epoxy resin modified polyol comprises bisphenol A type epoxy resin. Through the above technical scheme, the problems of low strength, high shrinkage rate and low foaming rate of polyurethane foam plugging material in the related art are solved.

Description

Technical Field

[0001] The invention relates to the technical field of polyurethane materials, and in particular to an epoxy resin modified polyurethane foaming plugging material and a preparation method thereof. Background Art

[0002] Polyurethane foam plugging material is a polymer material made by reacting raw materials such as isocyanate and polyether or polyester polyol. It will produce foam by chemical reaction during use. These foams can expand quickly and fill gaps and holes, so as to achieve the effect of plugging and stopping water. Polyurethane foam is widely used in plugging projects due to its excellent foaming, adhesion and sealing properties. However, traditional polyurethane foam materials still have problems such as insufficient strength, high shrinkage rate and low foaming rate in plugging applications. The low strength of the material not only cannot withstand the sealing requirements under high pressure, but also easily leads to poor plugging effect and poor durability. The high shrinkage rate will also produce new leakage channels, resulting in reduced sealing effect and even cracks. The low foaming rate will cause the material to be unable to completely block the cracks, allowing water to continue to flow in the gaps and unable to form an effective sealing barrier. Therefore, it is very necessary to develop a polyurethane foam plugging material with high strength, low shrinkage rate and high foaming rate. Summary of the invention

[0003] The invention provides an epoxy resin modified polyurethane foam plugging material and a preparation method thereof, which solves the problems of low strength, high shrinkage rate and low foaming rate of the polyurethane foam plugging material in the related art.

[0004] The technical scheme of the present invention is as follows: The present invention proposes an epoxy resin modified polyurethane foam plugging material, comprising component A and component B, wherein component A comprises the following component raw materials in parts by weight: 70 to 90 parts of polyether polyol, 10 to 30 parts of epoxy resin modified polyol, 2 to 4 parts of foaming agent, 0.5 to 1.5 parts of catalyst A, 0.5 to 1.5 parts of surfactant, and 8 to 10 parts of auxiliary agent, and component B is polymethylene polyphenyl polyisocyanate; the epoxy resin in the raw materials of the epoxy resin modified polyol comprises bisphenol A type epoxy resin.

[0005] As a further technical solution, the polyol in the epoxy resin modified polyol includes one or more of glycerol, ethylene glycol, and propylene glycol.

[0006] As a further technical solution, the NCO index of the component A and the component B when mixed is 110-140.

[0007] As a further technical solution, the calculation formula of the NCO index is: NCO index=100×NCO equivalent number / OH equivalent number.

[0008] In the present invention, epoxy resin is used to modify polyol. By introducing epoxy resin into the polyurethane system and adjusting the size of the NCO index, the cohesion of the plugging material is enhanced, the pores and micro defects inside the material are reduced, the polymerization reaction and foaming process of the polyurethane are promoted, the strength of the polyurethane foam plugging material is further improved, the shrinkage rate is reduced, and the foaming rate is increased.

[0009] As a further technical solution, the mass ratio of epoxy resin to polyol in the raw materials of the epoxy resin-modified polyol is 10:1-5.

[0010] As a further technical solution, the preparation method of the epoxy resin modified polyol comprises the following steps: weighing epoxy resin and polyol, adding them into a solvent, mixing them evenly, and performing a ring-opening reaction under the action of a catalyst B to obtain the epoxy resin modified polyol.

[0011] As a further technical solution, the solvent includes one or two of ethanol and xylene.

[0012] As a further technical solution, the mass of the solvent is 5% to 10% of the total mass of the epoxy resin, the polyol and the catalyst.

[0013] As a further technical solution, after the mixing is uniform, the obtained mixture is heated to 80-120°C at a heating rate of 2-3°C / min, and then kept warm under the action of a catalyst for a ring-opening reaction.

[0014] As a further technical solution, the insulation time is 2 to 4 hours.

[0015] As a further technical solution, the catalyst B is boron trifluoride etherate.

[0016] As a further technical solution, the added amount of the catalyst B is 0.1% to 0.5% of the mass of the epoxy resin.

[0017] As a further technical solution, the catalyst A includes one or both of an amine catalyst and an organic tin catalyst.

[0018] As a further technical solution, when the catalyst A is composed of an amine catalyst and an organotin catalyst, the mass ratio of the amine catalyst to the organotin catalyst is 5:2-3.

[0019] In the present invention, an amine catalyst and an organic tin catalyst are added at the same time to exert the synergistic effect of the two, improve the catalytic activity, optimize the foaming process of the plugging material, maintain a stable reaction rate, make the generated bubbles uniform in size and regularly distributed, and thus obtain a polyurethane foam with a good pore structure, thereby enhancing the strength of the polyurethane foam plugging material, reducing the shrinkage rate, and improving the foaming rate.

[0020] As a further technical solution, the amine catalyst includes one or more of triethylenediamine, triethylamine, and tetramethylethylenediamine, and the organic tin catalyst includes one or more of dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin dioctoate.

[0021] As a further technical solution, at least one of the following technical features is also included: The foaming agent is water; The surfactant includes one or two of polydimethylsiloxane and methylphenyl silicone oil; The auxiliary agent includes one or more of an antioxidant, a flame retardant, and a filler.

[0022] As a further technical solution, the epoxy resin also includes bisphenol F epoxy resin. When the epoxy resin is composed of bisphenol A epoxy resin and bisphenol F epoxy resin, the mass ratio of the bisphenol A epoxy resin to the bisphenol F epoxy resin is 7:2~3.

[0023] In the present invention, bisphenol A epoxy resin and bisphenol F epoxy resin are added simultaneously as modifiers of the polyol to exert their synergistic effect, form a stable cross-linked structure in the plugging material matrix, and thus enhance the strength of the polyurethane foam plugging material, reduce the shrinkage rate, and improve the foaming rate.

[0024] The present invention also provides a method for preparing an epoxy resin modified polyurethane foam plugging material, comprising the following steps: S1. Weigh polyether polyol, epoxy resin modified polyol, foaming agent, surfactant, catalyst A and additives and mix to obtain component A; S2. Mix component A and component B to obtain polyurethane foam plugging material.

[0025] The working principle and beneficial effects of the present invention are: In the present invention, epoxy resin is introduced into the polyurethane system, and component A is obtained by mixing raw materials such as polyether polyol and epoxy resin modified polyol, and component B is taken as polymethylene polyphenyl polyisocyanate, so that an interpenetrating network structure is formed inside the polyurethane foam plugging material, thereby improving the strength and toughness of the plugging material, reducing shrinkage, and improving the foaming rate. DETAILED DESCRIPTION

[0026] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] In the following examples and comparative examples: Polyether polyol: molecular weight 4000g / mol, functionality 2, hydroxyl value 26.5~29.5mgKOH / g; Polymethylene polyphenyl polyisocyanate: model PM200, isocyanate content 30.5wt%~32.0wt%; Bisphenol A epoxy resin: model WQ-1228, epoxy equivalent weight 185~190g / eq; Bisphenol F type epoxy resin: model is NPEF-164X, epoxy equivalent is 185~205g / eq.

[0028] Example 1 The preparation method of epoxy resin modified polyol comprises the following steps: weighing 100 parts of epoxy resin and 10 parts of glycerol, adding 5.5 parts of ethanol, heating to 80°C and stirring under nitrogen protection, controlling the heating rate to be 3°C / min, adding 0.1 parts of boron trifluoride ether complex, keeping the temperature at 80°C for reaction for 4 hours, cooling and discharging to obtain epoxy resin modified polyol, wherein the epoxy resin is bisphenol A type epoxy resin; A method for preparing an epoxy resin modified polyurethane foam plugging material comprises the following steps: S1. Weigh 70 parts of polyether polyol, 10 parts of epoxy resin modified polyol, 2 parts of water, 0.5 parts of polydimethylsiloxane and 0.5 parts of triethylenediamine and mix them to obtain component A; S2. Mix component A with polymethylene polyphenyl polyisocyanate to obtain a polyurethane foam plugging material, wherein the NCO index of component A after mixing with polymethylene polyphenyl polyisocyanate is 110.

[0029] Example 2 The preparation method of epoxy resin modified polyol comprises the following steps: weighing 100 parts of epoxy resin and 30 parts of ethylene glycol, adding 10.42 parts of ethanol, heating to 100°C and stirring under nitrogen protection, controlling the heating rate to be 3°C / min, adding 0.3 parts of boron trifluoride ether complex, keeping the temperature at 100°C for reaction for 3 hours, cooling and discharging to obtain epoxy resin modified polyol, wherein the epoxy resin is bisphenol A type epoxy resin; A method for preparing an epoxy resin modified polyurethane foam plugging material comprises the following steps: S1. Weigh 80 parts of polyether polyol, 20 parts of epoxy resin modified polyol, 3 parts of water, 1 part of polydimethylsiloxane and 1 part of triethylamine and mix them to obtain component A; S2. Mix component A with polymethylene polyphenyl polyisocyanate to obtain a polyurethane foam plugging material, wherein the NCO index of component A after mixing with polymethylene polyphenyl polyisocyanate is 110.

[0030] Example 3 The preparation method of epoxy resin modified polyol comprises the following steps: weighing 100 parts of epoxy resin and 50 parts of propylene glycol, adding 15.05 parts of ethanol, heating to 120°C and stirring under nitrogen protection, controlling the heating rate to be 3°C / min, adding 0.5 parts of boron trifluoride ether complex, keeping the temperature at 120°C for reaction for 2 hours, cooling and discharging to obtain epoxy resin modified polyol, wherein the epoxy resin is bisphenol A type epoxy resin; A method for preparing an epoxy resin modified polyurethane foam plugging material comprises the following steps: S1. Weigh 90 parts of polyether polyol, 30 parts of epoxy resin modified polyol, 4 parts of water, 1.5 parts of methylphenyl silicone oil and 1.5 parts of tetramethylethylenediamine and mix them to obtain component A; S2. Mix component A with polymethylene polyphenyl polyisocyanate to obtain a polyurethane foam plugging material, wherein the NCO index of component A after mixing with polymethylene polyphenyl polyisocyanate is 110.

[0031] Example 4 Compared with Example 1, the difference of Example 4 is that the NCO index of component A after mixing with polymethylene polyphenyl polyisocyanate is 120.

[0032] Example 5 Compared with Example 1, the difference of Example 5 is that the NCO index of component A after mixing with polymethylene polyphenyl polyisocyanate is 130.

[0033] Example 6 Compared with Example 1, the difference of Example 6 is that the NCO index of component A after mixing with polymethylene polyphenyl polyisocyanate is 140.

[0034] Example 7 Compared with Example 5, Example 7 is different in that triethylenediamine is replaced by an equal amount of dibutyltin dilaurate.

[0035] Example 8 Compared with Example 5, Example 8 is different in that triethylenediamine is replaced by triethylenediamine and dibutyltin dilaurate in a mass ratio of 5:2.

[0036] Example 9 Compared with Example 5, Example 9 is different in that triethylenediamine is replaced by triethylenediamine and dibutyltin dilaurate in a mass ratio of 5:3.

[0037] Example 10 Compared with Example 9, the difference in Example 10 is that the epoxy resin is bisphenol F type epoxy resin.

[0038] Embodiment 11 Compared with Example 9, the difference of Example 11 is that the epoxy resin consists of bisphenol A epoxy resin and bisphenol F epoxy resin in a mass ratio of 7:2.

[0039] Example 12 Compared with Example 9, the difference of Example 12 is that the epoxy resin consists of bisphenol A epoxy resin and bisphenol F epoxy resin in a mass ratio of 7:3.

[0040] Comparative Example 1 A method for preparing an epoxy resin modified polyurethane foam plugging material comprises the following steps: S1. Weigh 70 parts of polyether polyol, 10 parts of glycerol, 2 parts of water, 0.5 parts of polydimethylsiloxane, and 0.5 parts of triethylenediamine and mix them to obtain component A; S2. Mixing component A with polymethylene polyphenyl polyisocyanate to obtain a polyurethane foam plugging material, wherein the NCO index of component A when mixed with polymethylene polyphenyl polyisocyanate is 110.

[0041] The polyurethane foam plugging materials prepared in Examples 1 to 12 and Comparative Example 1 were tested according to the following method: 1. Compression strength: Test the compression strength of the sample according to the compression strength test method specified in GB / T 8813-2020 "Determination of compression properties of rigid foam plastics".

[0042] 2. Foaming rate: Test the foaming rate of the sample according to the test method for hydrophobic foaming rate specified in JC / T 2041-2020 "Polyurethane Grouting Materials".

[0043] The test results are shown in the following table: Table 1 Performance test results of polyurethane foam plugging materials prepared in Examples 1 to 12 and Comparative Example 1

[0044] Compared with Comparative Example 1, Example 1 adds epoxy resin-modified polyol modified by epoxy resin. As a result, the compressive strength and foaming rate of Example 1 are better than those of Comparative Example 1, indicating that when epoxy resin-modified polyol modified by epoxy resin is added, the strength and foaming rate of the polyurethane foam plugging material can be improved.

[0045] Compared with Example 1, the NCO index of component A in Examples 4 to 6 when mixed with polymethylene polyphenyl polyisocyanate is different. As a result, the compressive strength and foaming rate of Examples 4 and 5 are better than those of Examples 1 and 6, indicating that when the NCO index of component A when mixed with polymethylene polyphenyl polyisocyanate is 120 to 130, the strength and foaming rate of the polyurethane foam plugging material can be improved.

[0046] Compared with Example 5, Examples 8 and 9 simultaneously added amine catalysts and organotin catalysts. As a result, the compressive strength and foaming rate of Examples 8 and 9 were better than those of Example 5, indicating that the amine catalysts and organotin catalysts play a synergistic role and can further improve the strength and foaming rate of the polyurethane foam plugging material.

[0047] Compared with Examples 9 and 10, Examples 11 and 12 simultaneously add bisphenol A epoxy resin and bisphenol F epoxy resin. As a result, the compressive strength and foaming rate of Examples 11 and 12 are better than those of Examples 9 and 10, indicating that bisphenol A epoxy resin and bisphenol F epoxy resin play a synergistic role and can further improve the strength and foaming rate of the polyurethane foam plugging material.

[0048] The shrinkage rate and foaming time of the polyurethane foam plugging material prepared in Example 12 were also tested. The results showed that the shrinkage rate of Example 12 was ≤1%, the dimensional stability was good, the initial foaming time when exposed to water was 30s, and the curing time was 300s, which met the requirements for rapid construction of plugging.

[0049] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. An epoxy resin modified polyurethane foam plugging material, characterized in that: The invention comprises component A and component B, wherein component A comprises the following raw materials in parts by weight: 70-90 parts of polyether polyol, 10-30 parts of epoxy resin modified polyol, 2-4 parts of foaming agent, 0.5-1.5 parts of catalyst A, 0.5-1.5 parts of surfactant and 8-10 parts of auxiliary agent; component B is polymethylene polyphenyl polyisocyanate; and the epoxy resin in the raw materials of the epoxy resin modified polyol comprises bisphenol A type epoxy resin.

2. The epoxy resin modified polyurethane foam plugging material according to claim 1, characterized in that: The polyol in the epoxy resin modified polyol includes one or more of glycerol, ethylene glycol and propylene glycol.

3. The epoxy resin modified polyurethane foam plugging material according to claim 1, characterized in that: The NCO index of the A component and the B component when mixed is 110-140.

4. The epoxy resin modified polyurethane foam plugging material according to claim 1, characterized in that: The mass ratio of epoxy resin to polyol in the raw materials of the epoxy resin-modified polyol is 10:1-5.

5. The epoxy resin modified polyurethane foam plugging material according to claim 1, characterized in that: The catalyst A includes one or both of an amine catalyst and an organic tin catalyst.

6. The epoxy resin modified polyurethane foam plugging material according to claim 5, characterized in that: When the catalyst A is composed of an amine catalyst and an organotin catalyst, the mass ratio of the amine catalyst to the organotin catalyst is 5:2-3.

7. The epoxy resin modified polyurethane foam plugging material according to claim 5, characterized in that: The amine catalyst includes one or more of triethylenediamine, triethylamine, and tetramethylethylenediamine, and the organic tin catalyst includes one or more of dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin dioctoate.

8. The epoxy resin modified polyurethane foam plugging material according to claim 1, characterized in that: It also includes at least one of the following technical features: The foaming agent is water; The surfactant includes one or two of polydimethylsiloxane and methylphenyl silicone oil; The auxiliary agent includes one or more of an antioxidant, a flame retardant, and a filler.

9. The epoxy resin modified polyurethane foam plugging material according to claim 1, characterized in that: The epoxy resin also includes bisphenol F epoxy resin. When the epoxy resin is composed of bisphenol A epoxy resin and bisphenol F epoxy resin, the mass ratio of the bisphenol A epoxy resin to the bisphenol F epoxy resin is 7:2-3.

10. The method for preparing an epoxy resin modified polyurethane foam plugging material according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1. Weigh polyether polyol, epoxy resin modified polyol, foaming agent, surfactant, catalyst A and additives and mix to obtain component A; S2. Mix component A and component B to obtain polyurethane foam plugging material.

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