Degradable epoxy resin composition, winding resin, application and preparation method

Abstract

The invention discloses a degradable epoxy resin composition, which is prepared from the following components in parts by weight: 40 to 100 parts of epoxy resin, 0 to 20 parts of modified epoxy resin and 0 to 60 parts of degradable epoxy resin. The degradable winding resin composite material prepared from the degradable epoxy resin composition can realize degradation and stripping of reinforced fibers under mild conditions, realizes recycling, and reduces environmental protection pressure. Under the combined action of the degradable epoxy resin composition, the anhydride curing agent and the defoaming agent, the epoxy resin can be applied to a winding process, and the prepared composite material is excellent in boiling resistance and high temperature resistance. The degradable winding resin composite material also has a flame retardant effect, and has good tensile strength and shear strength.

Description

Technical Field

[0001] The invention relates to the field of polymer compounds, and in particular to a degradable epoxy resin composition, a winding resin, and an application and preparation method thereof. Background Art

[0002] The winding process is a process in which continuous fibers (or cloth tapes, prepreg yarns) soaked in resin glue are wound onto a core mold according to a certain pattern, and then cured, demolded, and other steps are performed to finally obtain a product of the desired shape. The fiber winding molding designs the winding pattern according to the stress conditions of the product, which can give full play to the strength of the fiber. The winding process requires winding stress, so a higher balance is required between the strength and toughness of the epoxy resin. After being prepared into a product, the cured product is difficult to degrade and recycle, which puts great pressure on the sustainable development of energy. Therefore, it is very important to develop a degradable resin that can be processed by the winding process.

[0003] Chinese invention patent CN118834371A discloses a high Tg value degradable thermosetting composite material and a degradable downhole plugging tool prepared therefrom. A flexible epoxy resin, a main catalyst and an alicyclic anhydride crosslinking agent are used as raw materials to prepare a high Tg value degradable thermosetting composite material. It is degradable at an extremely low temperature of 95°C, but the hot molding process is used, and it will not be subjected to force during the processing, which affects the mechanical strength of the product. Chinese invention patent CN103517947B discloses a reinforced composite material and a recycling method thereof, comprising a reinforcing material and a cross-linked epoxy resin matrix. The recycling method of the fiber-reinforced composite material can be carried out under relatively mild reaction conditions, but the mechanical strength resistant to high temperatures is poor. Summary of the invention

[0004] In order to develop a degradable resin that can be processed by winding technology, the first aspect of the present invention provides a degradable epoxy resin composition, which includes 40-100 parts of epoxy resin, 0-20 parts of modified epoxy resin, and 0-60 parts of degradable epoxy resin, and the weight part is not 0.

[0005] As a preferred embodiment, the molecular formula of the degradable epoxy resin is as follows:

[0006]

[0007] Where n is a natural number.

[0008] As a preferred embodiment, the modified epoxy resin is selected from at least one of polyurethane-modified epoxy resin, acrylic-modified epoxy resin, epoxy-acrylic-modified epoxy resin, phenol-modified epoxy resin, and silicone-modified epoxy resin.

[0009] As a preferred embodiment, the epoxy resin includes but is not limited to one or a combination of bisphenol A epoxy resin, bisphenol S epoxy resin, and bisphenol F epoxy resin.

[0010] The second aspect of the present invention provides a degradable winding resin. The raw materials for its preparation include 40-60 parts of the above-mentioned degradable epoxy resin composition, 30-70 parts of a curing agent, 0-5 parts of a defoaming agent, and 0-20 parts of a filler, in parts by weight, and the weight ratio is not 0.

[0011] As a preferred embodiment, the curing agent is an anhydride curing agent, and the anhydride curing agent is selected from at least one of methyltetrahydrophthalic anhydride (MeTHPA), methylhexahydrophthalic anhydride (MeHHPA), methylnadic anhydride (MNA), dodecylsuccinic anhydride (DDSA), and chlorendic anhydride (HET).

[0012] As a preferred embodiment, the defoamer is an epoxy defoamer, and the epoxy equivalent of the defoamer is 250-320 g / eq.

[0013] As a preferred embodiment, the filler is selected from at least one of an inorganic filler, a synthetic rubber, a thermoplastic resin, and a flexible chain curing agent.

[0014] The third aspect of the present invention provides a degradable winding resin composite material, which comprises 20-40% of the above-mentioned degradable winding resin and 60-80% of a fiber reinforcement material, based on the weight percentage of the degradable winding resin composite material.

[0015] As a preferred embodiment, the fiber reinforcement material is selected from at least one of glass fiber, carbon fiber, aramid fiber and basalt fiber.

[0016] As a preferred embodiment, the viscosity of the degradable winding resin composite material at 25° C. is 400-1200 cps; and the glass transition temperature Tg of the resin component measured by differential scanning calorimetry DSC is 90-150° C.

[0017] As a preferred embodiment, the degradable winding resin composite material is heated and degraded with an amine compound under alkaline conditions to strip the fibers.

[0018] As a preferred embodiment, the temperature of the heating degradation is 60-200° C., and the degradation time is 1-48 hours.

[0019] A fourth aspect of the present invention provides a method for preparing a degradable winding resin composite material, comprising the following steps:

[0020] S1. Melting and mixing a degradable epoxy resin composition, a curing agent, a defoaming agent, and a filler to prepare a degradable winding resin;

[0021] S2 mixes the biodegradable winding resin with the fiber reinforcement material and processes it using the winding process;

[0022] S3 is cured and set.

[0023] As a preferred implementation, the winding speed of the winding process is 10-30rpm, and the winding tension is 10-30N.

[0024] As a preferred embodiment, the specific parameters of the curing and setting are: first heating to 70-90° C., curing for 1-3 hours, then heating to 110-130° C., curing for 2-4 hours.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] (1) The degradable winding resin composite material of the present invention contains a degradable epoxy resin composition, which can be degraded under mild conditions, stripped of reinforcing fibers, and recycled, thereby reducing environmental pressure.

[0027] (2) The degradable winding resin composite material of the present invention adopts the degradable epoxy resin composition, anhydride curing agent and defoaming agent to realize the application of epoxy resin in the winding process. The prepared composite material has excellent water boiling resistance and high temperature resistance.

[0028] (3) The degradable winding resin composite material of the present invention can improve the flame retardant properties of the composite material by introducing 10% aluminum hydroxide into the system without causing adverse effects on the mechanical properties of the system.

[0029] (4) The degradable winding resin composite material of the present invention can directly replace the traditional epoxy resin during winding process, without the need to introduce new equipment or change the process, and the processing cost is low.

[0030] (5) The biodegradable winding resin composite material of the present invention is prepared into a ring-shaped product by a winding process, which has good tensile strength and shear strength. After being boiled in boiling water, it still has good tensile strength and shear strength. DETAILED DESCRIPTION

[0031] Example 1

[0032] A degradable epoxy resin composition comprises, by weight, 55 parts of epoxy resin, 5 parts of modified epoxy resin and 40 parts of degradable epoxy resin.

[0033] The molecular formula of the degradable epoxy resin is as follows:

[0034]

[0035] n is 1-100.

[0036] The epoxy resin is bisphenol A epoxy resin NPEL-128, purchased from Nan Ya Plastics Industry Co., Ltd.

[0037] The modified epoxy resin is CY-184, purchased from Huntsman Corporation of the United States.

[0038] A degradable winding resin is prepared from raw materials, in parts by weight, including 44.7 parts of the above-mentioned degradable epoxy resin composition, 45 parts of a curing agent, 0.3 parts of a defoaming agent, and 10 parts of a filler.

[0039] The degradable epoxy resin composition is self-made.

[0040] The curing agent is methyltetrahydrophthalic anhydride, purchased from Zhejiang Alpha Chemical Technology Co., Ltd., with the brand name AMT-120.

[0041] The defoamer has an epoxy equivalent of 250-320 g / eq and is purchased from BYK Chemicals with the brand name BYK P-9920.

[0042] The filler is aluminum hydroxide, purchased from Albemarle, with the brand name of flame retardant 904.

[0043] A degradable winding resin composite material comprises, by weight percentage, 30% of the above-mentioned degradable winding resin and 70% of a fiber reinforcement material.

[0044] The fiber reinforcement material is carbon fiber TZ700S.

[0045] A method for preparing a degradable winding resin composite material comprises the following steps:

[0046] S1. Melting and mixing a degradable epoxy resin composition, a curing agent, a defoaming agent, and a filler to prepare a degradable winding resin;

[0047] S2 mixes the biodegradable winding resin with the fiber reinforcement material and processes it using the winding process;

[0048] S3 is cured and set.

[0049] The winding speed of the winding process is 15 rpm, and the winding tension is 20N.

[0050] The specific parameters of the curing and setting are: firstly heating to 80° C. and curing for 2 hours, then heating to 120° C. and curing for 3 hours.

[0051] Example 2

[0052] A degradable epoxy resin composition comprises, by weight, 50 parts of epoxy resin, 10 parts of modified epoxy resin and 40 parts of degradable epoxy resin.

[0053] A degradable winding resin is prepared by raw materials including, by weight, 45 parts of the above-mentioned degradable epoxy resin composition, 44.7 parts of a curing agent, 0.3 parts of a defoaming agent, and 10 parts of a filler.

[0054] A degradable winding resin composite material and a preparation method thereof, comprising, by weight percentage, 25% of the above-mentioned degradable winding resin and 75% of a fiber reinforcement material.

[0055] The fiber reinforcement material is carbon fiber SYT49S.

[0056] The winding speed of the winding process is 30 rpm, and the winding tension is 30N.

[0057] The specific parameters of the curing and setting are: firstly heating to 80° C. and curing for 2 hours, then heating to 115° C. and curing for 3 hours.

[0058] The rest of the implementation is the same as Example 1.

[0059] Example 3

[0060] A degradable epoxy resin composition comprises, by weight, 52 parts of epoxy resin, 10 parts of modified epoxy resin and 40 parts of degradable epoxy resin.

[0061] A degradable winding resin is prepared by raw materials including, by weight, 44.9 parts of the above-mentioned degradable epoxy resin composition, 44.9 parts of a curing agent, 0.2 parts of a defoaming agent, and 10 parts of a filler.

[0062] A degradable winding resin composite material and a preparation method thereof, comprising, by weight, 28% of the above-mentioned degradable winding resin and 72% of a fiber reinforcement material.

[0063] The fiber reinforcement material is carbon fiber SYT49S.

[0064] The winding speed of the winding process is 30 rpm, and the winding tension is 30N.

[0065] The specific parameters of the curing and setting are: firstly heating to 75° C. and curing for 2 hours, then heating to 125° C. and curing for 3 hours.

[0066] The rest of the implementation is the same as Example 1.

[0067] Example 4

[0068] A degradable epoxy resin composition comprises, by weight, 55 parts of epoxy resin, 5 parts of modified epoxy resin and 40 parts of degradable epoxy resin.

[0069] A degradable winding resin is prepared by raw materials including, by weight, 47 parts of the above-mentioned degradable epoxy resin composition, 48 parts of a curing agent, 0 parts of a defoaming agent, and 5 parts of a filler.

[0070] A degradable winding resin composite material and a preparation method thereof, comprising, by weight percentage, 32% of the above-mentioned degradable winding resin and 68% of a fiber-reinforced material

[0071] The fiber reinforcement material is carbon fiber TZ700S.

[0072] The winding speed of the winding process is 30 rpm, and the winding tension is 30N.

[0073] The specific parameters of the curing and setting are: firstly heating to 85° C. and curing for 2 hours, then heating to 135° C. and curing for 2 hours.

[0074] The rest of the implementation is the same as Example 1.

[0075] Example 5

[0076] A degradable epoxy resin composition comprises, by weight, 55 parts of epoxy resin, 5 parts of modified epoxy resin and 40 parts of degradable epoxy resin.

[0077] A degradable winding resin is prepared by raw materials including, by weight, 47 parts of the above-mentioned degradable epoxy resin composition, 48 parts of a curing agent, 0 parts of a defoaming agent, and 9 parts of a filler.

[0078] The filler includes DMMP and aluminum hydroxide in a weight ratio of 4:5. Aluminum hydroxide was purchased from Albemarle and the brand is flame retardant 904. DMMP was purchased from Qingdao Xuxin Chemical Co., Ltd.

[0079] A degradable winding resin composite material and a preparation method thereof, comprising, by weight percentage, 35% of the above-mentioned degradable winding resin and 65% of a fiber reinforcement material.

[0080] The fiber reinforcement material is glass fiber TM+468GS.

[0081] The winding speed of the winding process is 30 rpm, and the winding tension is 30N.

[0082] The specific parameters of the curing and setting are: firstly heating to 85° C. and curing for 2 hours, then heating to 135° C. and curing for 2 hours.

[0083] Comparative Example 1

[0084] A degradable winding resin composite material, the specific implementation manner is the same as that of Example 1, except that the degradable winding resin is replaced by bisphenol A epoxy resin purchased from Nan Ya Plastics Industrial Co., Ltd., brand NPEL-128.

[0085] Performance Testing

[0086] According to GB / T 1458 standard, NOL ring samples were prepared, with an inner diameter of 150±0.2mm, a width of 6±0.2mm, a tensile thickness of 1.5±0.1mm, and a shear thickness of 3±0.1mm; the flat plate was wound into a 250mm long, 250mm wide, 2mm thick flat plate, and then a 0° tensile test specimen was prepared according to ISO 527-5. Examples 1, 3, and 5 were prepared into NOL rings, Example 2 was prepared into a wound plate, Example 4 was prepared into a wound gas cylinder, and Comparative Example 1 was prepared into a NOL ring. “ / ” indicates that different products have different test items for different application scenarios.

[0087] Table 1

[0088]

[0089]

Claims

1. A degradable epoxy resin composition, characterized in that: Calculated in parts by weight, it includes 40-100 parts of epoxy resin, 0-20 parts of modified epoxy resin, and 0-60 parts of degradable epoxy resin, and the weight part is not 0.

2. The degradable epoxy resin composition according to claim 1, characterized in that: The molecular formula of the degradable epoxy resin is as follows: Where n is a natural number.

3. The degradable epoxy resin composition according to claim 1, characterized in that: The modified epoxy resin is selected from at least one of polyurethane modified epoxy resin, acrylic modified epoxy resin, epoxy acrylic modified epoxy resin, phenolic modified epoxy resin and silicone modified epoxy resin.

4. A degradable winding resin, characterized in that: The raw materials for preparation include 40-60 parts of the degradable epoxy resin composition described in any one of claims 1-3, 30-70 parts of a curing agent, 0-5 parts of a defoaming agent, and 0-20 parts of a filler in parts by weight, and the weight part is not 0.

5. The degradable winding resin according to claim 4, characterized in that: The curing agent is an acid anhydride curing agent, and the acid anhydride curing agent is selected from at least one of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecylsuccinic anhydride, and chlorendic anhydride.

6. The degradable winding resin according to claim 4, characterized in that: The defoamer is an epoxy defoamer, and the epoxy equivalent of the defoamer is 250-320 g / eq.

7. The degradable winding resin according to claim 4, characterized in that: The filler is selected from at least one of inorganic fillers, synthetic rubber, thermoplastic resin, and flexible chain curing agent.

8. A degradable winding resin composite material, characterized in that: Calculated by weight percentage of the degradable winding resin composite material, the degradable winding resin according to any one of claims 4 to 7 comprises 20-40% and the fiber reinforcement material comprises 60-80%.

9. A method for preparing the degradable winding resin composite material according to claim 8, characterized in that: The following steps are involved: S1. Melting and mixing a degradable epoxy resin composition, a curing agent, a defoaming agent, and a filler to prepare a degradable winding resin; S2 mixes the biodegradable winding resin with the fiber reinforcement material and processes it using the winding process; S3 is cured and set.

10. The method for preparing the degradable winding resin composite material according to claim 9, characterized in that: The winding speed of the winding process is 10-30 rpm, and the winding tension is 10-30N.

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