阅读说明：本技术 一种定向断键降解复合材料并从中回收纤维的方法 (A method of orientation scission of link degrading composite and therefrom recycled fiber ) 是由 黄志雄 邓宗义 郭冬云 石敏先 刘晓帆 王大岗 于 2019-08-28 设计创作，主要内容包括：本发明提供一种定向断键降解复合材料并从中回收纤维的方法,该方法包括以下步骤：1)将复合材料切割成目标尺寸的复合材料方块,备用；2)将复合材料方块、溶剂、金属盐、配体、pH调节剂、氧化剂混合均匀后,进行加热处理,待复合材料块降解完全后,自然冷却至室温,然后,高速离心分离,得到纤维粗品；3)将纤维粗品洗涤并烘干,最后得纤维精品。本发明通过热溶剂效应和不饱和络合及弱络合作用,将溶剂、金属盐、配体、pH调节剂、氧化剂和复合材料混合后,进行加热处理,实现树脂的定向断键降解,最后得到表面树脂残留极少,基本无缺损,纤维强度保留率高达97.1％的纤维,且本发明中树脂的降解率高达100％。(The present invention provides a kind of orientation scission of link degrading composite and the therefrom method of recycled fiber, method includes the following steps: 1) composite material is cut into the composite material square of target size, it is spare；2) after mixing by composite material square, solvent, metal salt, ligand, pH adjusting agent, oxidant, heated, after material block degradation completely to be composite, then cooled to room temperature is centrifuged at a high speed, obtain fiber crude product；3) fiber crude product is washed and is dried, finally obtain fiber fine work.The present invention passes through hot solvent effect and unsaturated complexing and weak complexing effect, after solvent, metal salt, ligand, pH adjusting agent, oxidant and composite material are mixed, heated, realize the orientation scission of link degradation of resin, it is few to finally obtain surface resin residual, basic N/D, fibre strength retention rate are up to 97.1% fiber, and the degradation rate of resin is up to 100% in the present invention.)

1. a kind of orientation scission of link degrading composite and the therefrom method of recycled fiber, which comprises the following steps:

1) fiber reinforced thermosetting resin based composites are cut to conform to the square of size requirement, it is spare；

2) by the fiber reinforced thermosetting resin based composites square, solvent, metal salt, ligand, pH adjusting agent, oxidant After being sufficiently mixed, heated, after composite material square degradation completely, cooled to room temperature, then, centrifugation Separation, obtains fiber crude product；

3) by fiber crude product washing, drying to get fiber fine work.

2. orientation scission of link degrading composite according to claim 1 and the therefrom method of recycled fiber, which is characterized in that Solvent described in every 100mL in the step 2), the fiber reinforced thermosetting resin based composites square are 0.1~500g, The metal salt is 0.1~100g or 0.1~100ml, and the ligand is 0.1~100g or 0.1~100ml, and the pH is adjusted Agent is 0.1~100g or 0.1~100ml, and the oxidant is 0.1~1000g or 0.1~1000mL.

3. orientation scission of link degrading composite according to claim 1 and the therefrom method of recycled fiber, which is characterized in that The heating temperature of heat treatment described in the step 2) is 20~500 DEG C, and heating time is 0.1~120h.

4. orientation scission of link degrading composite according to claim 1 and the therefrom method of recycled fiber, which is characterized in that Solvent described in the step 2) be water, alcohols and its derivative, alkanes and its derivative, cycloalkane and its derivative, Ethers and its derivative, acetals and its derivative, carboxylic acids and its derivative, anhydride and its derivative, esters and its spread out Biology, phenols and its derivative, ketone and its derivative, arene and its derivative, polyfunctional group class solvent, nitrogenous chemical combination One or more combinations of species solvent and sulfur-containing compound class solvent.

5. orientation scission of link degrading composite according to claim 1 and the therefrom method of recycled fiber, which is characterized in that Metal salt described in the step 2) is molysite, ferrous salt, ferric salt, cobalt salt, sub- cobalt salt, high cobalt salt, nickel salt, sub- nickel salt, height Nickel salt, zinc salt, silver salt, aluminium salt, mercury salt, mantoquita, cuprous salt, lead salt, palladium salt, platinum salt, manganese salt, manganous salt, high manganese salt, cadmium salt, One or more combinations of bismuth salt, magnesium salts, calcium salt, chromic salts, zirconates, titanium salt.

6. orientation scission of link degrading composite according to claim 1 and the therefrom method of recycled fiber, which is characterized in that Ligand described in the step 2) is ammonium hydroxide, ethylenediamine tetra-acetic acid and edetate, acetylacetone,2,4-pentanedione, oxalic acid and solubility Oxalates, organic amine and its derivative, alkali metal hydroxide, soluble alkaline earth hydroxide, halogen acids and solubility Halogen acid salt, cyanide, rhodanide, isothiocyanate, alcohols and its derivative, ethers and its derivative, carboxylic acids and its One or more combinations of derivative.

7. orientation scission of link degrading composite according to claim 1 and the therefrom method of recycled fiber, which is characterized in that PH adjusting agent described in the step 2) is ammonium hydroxide, alkali metal oxide and hydroxide, alkaline earth oxide and hydroxide Object, soluble phosphate and hydrophosphate, soluble carbonate salt and bicarbonate, organic amine and its derivative, dilute sulfuric acid, salt One or more combinations of acid, organic acid.

8. orientation scission of link degrading composite according to claim 1 and the therefrom method of recycled fiber, which is characterized in that Step 2) the oxidant is the concentrated sulfuric acid, nitric acid and nitrate, nitrous acid and nitrite, more nitro compounds, hydrogen peroxide, secondary Hydracid and hypohalite, halous acid and halous acid salt, hydracid and halate, high hydracid and perhalide, permanganic acid and permanganic acid Salt, oxalic acid and oxalates, dichromic acid and bichromate, ferric acid and ferrate, bismuthic acid and bismuthates, persulfuric acid and persulfuric acid One or more combinations of salt, thiosulfate.

9. orientation scission of link degrading composite according to claim 1 and the therefrom method of recycled fiber, which is characterized in that Washing described in the step 3) includes: the in the mixed solvent ultrasound immersion 5 that the fiber crude product is placed in tetrahydrofuran and acetone ~1200min, then with the rinsing of the mixed solution of water and ethyl alcohol for several times to neutral.

10. orientation scission of link degrading composite according to claim 1 and therefrom the method for recycled fiber, feature exist In the drying temperature of drying described in the step 3) is 20~400 DEG C, and drying time is 0.5~72h.

Technical field

The present invention relates to fiber recovery technical fields, in particular to a kind of from fiber reinforced thermosetting resin based composites The method of middle recycled fiber.

Background technique

An important branch of the fiber reinforced thermosetting resin based composites as composite material, ratio small with density Intensity is high, specific modulus is big, corrosion resistance is strong, creep resistant and fatigue resistance are excellent, material, structure and performance designability by force, at The advantages that type good manufacturability, strong structure size stability.Thus, it is widely used in aerospace, wind electricity blade, traffic fortune The fields such as defeated, Leisure Sport, building, electric, medical instrument, pressure vessel.Also, its purposes is still constantly expanding, and uses Amount is also continuing to increase.

Fiber reinforced thermosetting resin based composites can generate more preimpregnation in prepreg production and process Expect waste material, the wastes such as a large amount of leftover pieces can be also generated in forming process.Additionally, due to the fiber reinforcement heat being largely on active service Thermosetting resin based composites material will be scrapped retired or be regenerated, though it is foreseeable that will generate a large amount of fiber reinforcement heat Thermosetting resin based composites waste.

Fiber used in fiber reinforced thermosetting resin based composites have high value, Gao Chengben, highly energy-consuming spy Point, therefore dimension enhancing thermosetting resin base composite scrap object is degraded and recycled and has very high economic benefit and ring It supports value value.In addition, more and more countries have put into effect for fiber reinforced thermosetting resin based composites offal treatment Decree.Therefore, whether consider from economy, or environmental protection or legal perspective, to fiber reinforced thermosetting resin base composite wood Material degrade and recycled fiber is very necessary and important.

Fiber reinforced thermosetting resin based composites after solidification form three-dimensional crosslinked network, insoluble not melt, thus have There are stronger chemical stability and thermal stability, product size stability is big, resistance to acid and alkali and excellent solvent resistance, and is difficult to Carry out biodegrade.Therefore, it is difficult to be degraded simultaneously to fiber reinforced thermosetting resin based composites under mild conditions Recycling and reusing fiber.In addition, fiber reinforced thermosetting resin based composites are one kind by thermosetting resin, fiber and fill out Expect the multiphase solid material being combined, complicated composition.Also, it is often and the materials such as metal are processed into product jointly, these because Element further improve to fiber reinforced thermosetting resin based composites degrade and recycling and reusing fiber difficulty.

Currently, the recovery processing mode to fiber reinforced thermosetting resin based composites mainly has three classes: energy regenerating Method, physical mechanical absorption method and chemical recycling.Energy regenerating method is simple for process, but higher cost, and there are environment The drawbacks of pollution and the wasting of resources.Physical mechanical absorption method is a kind of method that the current country is widely used, simple process, recycling It is at low cost, but the fiber degree of being about recycled obviously shortens, and mechanical property is remarkably decreased, and seriously affects its recycling.Chemical recovery Method divides chemical-solvent method, fluidized bed process, Asia/supercritical fluid method and pyrolysismethod, these methods or complex process, reaction condition again Harsh, the high requirements on the equipment, safety is poor, and cost recovery is very high；Or energy consumption and material consumption it is big, especially organic solvent usage amount Greatly, not energy-efficient and environmental protection；Or the mechanical property of serious damage fiber, influence its recycling.In addition, it is fine to be degraded using chemical recycling When dimension enhancing thermosetting resin based composites, the random scission of link of thermosetting resin, liquid product complicated components are difficult to produce liquid phase Object carries out separating-purifying and recycles.Therefore, chemical recycling is also difficult to heavy industrialization application.

Therefore, develop that a kind of energy consumption and material consumption are low, thermosetting resin degradation rate is high, fiber mechanics strength retention ratio is high, work Skill is simple and easy, reaction condition is green mildly, orientation scission of link, liquid product component is simple, is easily achieved heavy industrialization answers Fiber recovery new method is very necessary and important.

Summary of the invention

In view of this, the present invention is directed to propose a kind of orientation scission of link degrading composite and the therefrom method of recycled fiber, To solve, energy consumption and material consumption are high, thermosetting resin degradation rate is low, fiber mechanics strength retention ratio is low, complex process, reaction condition Harshness, liquid product complicated components, is difficult to realize the problem of large-scale application at the random scission of link of thermosetting resin, utilizes hot solvent Effect and unsaturated complexing and weak complexing effect come degradation of fibers enhancing thermosetting resin based composites and recycled fiber, without Pretreatment, overall process only need a step.

To achieve the above object and effect, the invention provides the following technical scheme: a kind of orientation scission of link degrading composite And the therefrom method of recycled fiber, which comprises the following steps:

1) fiber reinforced thermosetting resin based composites are cut to conform to the square of size requirement, it is spare；

2) by the fiber reinforced thermosetting resin based composites square, solvent, metal salt, ligand, pH adjusting agent, oxygen After agent is sufficiently mixed, heated, after composite material square degradation completely, cooled to room temperature, then, Centrifuge separation, obtains fiber crude product；

3) by fiber crude product washing, drying to get fiber fine work.

According to the above scheme, solvent described in every 100mL in the step 2), the fiber reinforced thermosetting resin base composite wood Material square is 0.1~500g, and the metal salt is 0.1~100g or 0.1~100ml, and the ligand is 0.1~100g or 0.1 ~100ml, the pH adjusting agent be 0.1~100g or 0.1~100ml, the oxidant be 0.1~1000g or 0.1~ 1000mL。

According to the above scheme, the heating temperature of heat treatment described in the step 2) is 20~500 DEG C, and heating time is 0.1~120h.

According to the above scheme, solvent described in the step 2) be water, alcohols and its derivative, alkanes and its derivative, Cycloalkane and its derivative, ethers and its derivative, acetals and its derivative, carboxylic acids and its derivative, anhydride and Its derivative, esters and its derivative, phenols and its derivative, ketone and its derivative, arene and its derivative, more officials One or more combinations of class solvent, nitrogenous compound class solvent and sulfur-containing compound class solvent can be rolled into a ball.

According to the above scheme, metal salt described in the step 2) is molysite, ferrous salt, ferric salt, cobalt salt, sub- cobalt salt, height Cobalt salt, nickel salt, sub- nickel salt, high nickel salt, zinc salt, silver salt, aluminium salt, mercury salt, mantoquita, cuprous salt, lead salt, palladium salt, platinum salt, manganese salt, One or more combinations of manganous salt, high manganese salt, cadmium salt, bismuth salt, magnesium salts, calcium salt, chromic salts, zirconates, titanium salt.

According to the above scheme, ligand described in the step 2) is ammonium hydroxide, ethylenediamine tetra-acetic acid and edetate, second Acyl acetone, oxalic acid and Soluble oxalate salt, organic amine and its derivative, alkali metal hydroxide, soluble alkaline earth hydrogen-oxygen Compound, halogen acids and soluble halogen acid salt, cyanide, rhodanide, isothiocyanate, alcohols and its derivative, ethers and One or more combinations of its derivative, carboxylic acids and its derivative.

According to the above scheme, pH adjusting agent described in the step 2) is ammonium hydroxide, alkali metal oxide and hydroxide, alkaline earth Metal oxide and hydroxide, soluble phosphate and hydrophosphate, soluble carbonate salt and bicarbonate, organic amine and One or more combinations of its derivative, dilute sulfuric acid, hydrochloric acid, organic acid.

According to the above scheme, the step 2) oxidant be the concentrated sulfuric acid, nitric acid and nitrate, it is nitrous acid and nitrite, more Nitro compound, hydrogen peroxide, hypohalogenous acids and hypohalite, halous acid and halous acid salt, hydracid and halate, high hydracid and high halogen Hydrochlorate, permanganic acid and permanganate, oxalic acid and oxalates, dichromic acid and bichromate, ferric acid and ferrate, bismuthic acid and bismuth One or more combinations of hydrochlorate, persulfuric acid and persulfate, thiosulfate.

According to the above scheme, washing described in the step 3) includes: that the fiber crude product is placed in tetrahydrofuran and acetone In the mixed solvent ultrasound impregnates 5~1200min, then with the rinsing of the mixed solution of water and ethyl alcohol for several times to neutral.

According to the above scheme, the drying temperature of drying described in the step 3) be 20~400 DEG C, drying time be 0.5~ 72h。

Compared with the existing technology, a kind of orientation scission of link degrading composite of the present invention and the therefrom side of recycled fiber Method has the advantage that

1, a kind of orientation scission of link degrading composite of the invention and therefrom the method for recycled fiber passes through hot solvent effect It is acted on unsaturation complexing and weak complexing, after solvent, metal salt, ligand, pH adjusting agent, oxidant and composite material are mixed, Heated, realizes the orientation scission of link degradation of thermosetting resin, finally obtain surface resin residual seldom, it is substantially intact Damage, fibre strength retention rate is up to 97.1% fiber, and the degradation rate of resin is up to 100% in the present invention, liquid product group Divide simple, recycling easy to separate and purify；

2, the present invention acts on degrading composite and recycled fiber by hot solvent effect and unsaturated complexing and weak complexing, Reaction condition is mild, and low energy consumption for degradation, and does not need preprocessing, and overall process one-step method is completed, simple for process.Reaction condition It is easily controllable, pressure is carried by system, is not necessarily to Additional pressurizations, safety is good.In addition, the present invention it is environmentally friendly, substantially without Toxic gas release, reaction process are environmentally protective.And raw material is cheap and easily-available, and process cycle is short, industrial applications easy to accomplish.

Detailed description of the invention

The attached drawing for constituting a part of the invention is used to provide further understanding of the present invention, schematic reality of the invention It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:

Fig. 1 is carbon fiber/phenolic resin composite block photo described in the embodiment of the present invention 1；

Fig. 2 is using a kind of orientation scission of link degrading composite described in the embodiment of the present invention 1 and therefrom recycled fiber The photo of the carbon fiber of method recycling；

Fig. 3 is using a kind of orientation scission of link degrading composite described in the embodiment of the present invention 1 and therefrom recycled fiber The photo for the liquid product that method obtains；

Fig. 4 is the scanning electron microscope diagram of original carbon fiber described in the embodiment of the present invention 1；

Fig. 5 is using a kind of orientation scission of link degrading composite described in the embodiment of the present invention 1 and therefrom recycled fiber The scanning electron microscope diagram of the carbon fiber of method recycling.

Specific embodiment

In order to make technological means of the invention, creative feature, reach purpose and effect is simple and easy, below with reference to specific reality Mode is applied, the present invention is further elaborated on.It should be noted that the present invention includes but is not limited to following embodiment, do not rushing Under the premise of prominent, embodiment and its feature in the present invention be can be combined with each other.

Below with reference to drawings and examples, invention is further explained.