CN104804163A - Thermally-reversible covalent crosslinking agent as well as synthesis method and application thereof - Google Patents

Thermally-reversible covalent crosslinking agent as well as synthesis method and application thereof Download PDF

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CN104804163A
CN104804163A CN201510111733.7A CN201510111733A CN104804163A CN 104804163 A CN104804163 A CN 104804163A CN 201510111733 A CN201510111733 A CN 201510111733A CN 104804163 A CN104804163 A CN 104804163A
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organic solvent
synthetic method
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product
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孙平川
陈胜利
王粉粉
吴强
陈铁红
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Nankai University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
    • C07D491/18—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention provides a thermally-reversible covalent crosslinking agent as well as a synthesis method and an application thereof and relates to the field of macromolecules. The compound can be obtained through synthesis of diene with hydroxyl groups and dienophile with hydroxyl groups through a multi-step Diels-Alder reaction and a reverse reaction, a thermoset elastomer prepared from the compound used as a polyurethane crosslinking agent can be recycled with a universal macromolecular material processing forming method on the premise that the high mechanical property of resin is guaranteed, so that waste of energy and resources is reduced, and the material is recycled.

Description

A kind of Thermally reversible covalent crosslinking and synthetic method thereof and application
Technical field
The present invention relates to high polymer material technology, particularly a kind of synthetic method of Thermally reversible covalent crosslinking, and prepare the application in the thermosetting resin that can reprocess.
Background technology
Thermoset macromolecule material relies on its cross-linked network structure, usually has high rigidity, high strength, high solvent resistance, the performance that high-wearing feature etc. are outstanding, is widely used in building, machinery, aerospace and bio-medical field.But along with the consumption of the type material constantly increases, it uses the concern that the process problem after discarding causes people day by day, and the variations such as the waste of the resource brought therefrom and the destruction of environment are also needed badly to take effective measures and solved.Meanwhile, these problems limit again thermosetting resin conversely and expand use range further, make material cannot play its due value completely.
For tackling this predicament, scientific research personnel starts dynamic chemical key to be incorporated in crosslinked polymkeric substance, by under certain incentive condition, crosslinked macromolecular material can the defect that occurs of spontaneous healing material internal, after application completes, also again can be recovered utilization.In numerous dynamic chemical key systems, especially react with Diels-Alder the cross-linked network structure constructed extensively concerned, this is because the high efficiency of Diels-Alder reaction and validity, the polymer materials generally prepared thus all has good mechanical property.But, in the Diels-Alder reaction system reported before this, usually need to adopt complicated synthetic technology DA reaction monomers to be incorporated on the main chain of polymkeric substance, and this is difficult to realize usually in the industrial production.For improving this mentality of designing further, on the basis of patent CN103059250A, we propose technology of preparing of the present invention.
Summary of the invention
The object of this invention is to provide a kind of Thermally reversible covalent crosslinking, i.e. a kind of linking agent of thermosetting resin;
Object of the present invention also proposes a kind of synthetic method of above-mentioned linking agent;
Another object of the present invention is to provide the application of above-mentioned linking agent in thermal reversion cross-linked polyurethane.
Thermally reversible covalent crosslinking provided by the invention has following general formula:
Wherein, R 1=CH 2cH 2oH or CH 2cH (OH) CH 2oH or CH (CH 2oH) CH 2oH;
R 2=R 3=H, CH 2oH, CH (CH 3) OH or CH 2cH (CH 3) OH;
R 4=H or CH 2oH; Wherein R 2, R 3, R 4can not be H simultaneously.
Shown in the following four-step reaction of synthetic method that the invention provides this compounds:
Step 1: after maleic anhydride is dissolved in organic solvent, add furans, stirred at ambient temperature 24 hours, obtains white powdery solid TM-1 after reaction soln suction filtration, save backup after dry in vacuum drying oven in moisture eliminator.The mol ratio of furans and maleic anhydride should slightly larger than 1;
Step 2: get after TM-1 powder joins and stir in the round-bottomed flask that organic solvent is housed, dropwise add R by constant pressure funnel 1-NH 2solution (R 1-NH 2: TM-1=1.03:1), in dropping process, solution is clarified gradually, subsequently whole reaction unit be warming up to 85 DEG C backflow 8 hours, period solution colour gradually from colourless become orange-yellow.After having reacted, suction filtration can obtain white solid powder TM-2, in moisture eliminator saves backup after removing solvent in vacuum drying oven;
Step 3: weigh dried TM-2 and be dissolved in organic solvent, reflux at 110 DEG C 8h, need constantly to blast rare gas element to take away the furans deviate from reaction process, the filtrate having reacted rear filtered while hot gained is placed 12 hours in the refrigerator of 0 DEG C, generate white, needle-shaped crystals TM-3 gradually, dry after outwelling supernatant liquid;
Step 4: be connected with rare gas element and be equipped with in churned mechanically there-necked flask, add the solution of TM-3, then furan derivatives is added dropwise to, furan derivatives excessive 5% can be made in dropping process, then solution warms to 85 DEG C reaction 24 hours, the TM generated is deposited on flask inwall gradually, after question response completes and outwells supernatant liquid, can obtain white powder after product drying.
In the inventive method, described organic solvent can be polarity or non-polar solvent, as ethyl acetate, and tetrahydrofuran (THF), anhydrous diethyl ether, sherwood oil, toluene, methyl alcohol, ethanol, acetone, chloroform, dimethyl sulfoxide (DMSO), dioxane or normal hexane.
In the inventive method, described rare gas element is that nitrogen, argon gas etc. can the gases of starvation.
In the inventive method, described R 1-NH 2for thanomin, 3-amino-1,2-PD, the one in 2-amino-1,3-propanediol.
In the inventive method, furan derivatives is 2-furfuralcohol, 3-furfuralcohol, 1-(2-furyl) ethanol, 5-methyl-2-furfuralcohol, alpha-methyl-2-furans ethanol, the one in 2,5-FDM.
In described synthesis step 1, the mass fraction of each reactant is: furans is 92.5-95.3 part, maleic anhydride is 100 parts, solvent is 150-200 part;
In described synthesis step 2, the mass fraction of each reactant is: TM-1 is 100 parts, R 1-NH 2for 37.6-56 part, solvent are 200-300 part;
In described synthesis step 3, the mass fraction of each reactant is: TM-2 is 5 parts, solvent is 100-150 part;
In described synthesis step 4, the mass fraction of each reactant is: TM-3 is 100 parts, furan derivatives is 60-77 part, solvent is 1600-2000 part.
Adopt the product of gained of the present invention further can by the methods such as thin-layer chromatography, column chromatography or recrystallization separating-purifying in addition.As used the method for recrystallization, recommend the mixed solvent of the nonpolar and polar solvent adopted, as ethanol-sherwood oil, ethyl acetate-hexane, ethyl acetate-toluene.By the method for column chromatography and thin-layer chromatography, solvent used is the mixed solvent of polar solvent and non-polar solvent, recommends useable solvents to be methylene dichloride-normal hexane, ethyl acetate-hexane, ethyl acetate-light petrol, acetonitrile-sherwood oil.
Present invention also offers this compounds and prepare the application in crosslinked polyurethane elastomer body.By adding the poly-hydroxy linking agent of molten state in base polyurethane prepolymer for use as, under hot conditions, isocyanic ester and hydroxyl highly effective reaction form cross-linked network and prepare the crosslinked thermosetting polyurethane elastomer of thermal reversion.The method of this mass polymerization adds without the need to extra solvent, with low cost, simple to operate, is convenient to large-scale application.The thermosetting resin adopting such Thermally reversible covalent crosslinking to prepare is when temperature is higher than 120 DEG C, and cross-linked network dissociates, and forms linear oligomeric segment, is easy to forming process again.General polymer material molding working method can be adopted, as hot pressing formation process, injection moulding, solution film casting method etc., to discarded thermosetting material processing and utilization again.The appearance of this type of thermal reversion crosslinked polymeric materials, meeting people under the prerequisite of high performance material demand, decreasing the waste of resource and the energy, alleviating environmental stress, achieving the sustainable use of resource.
Accompanying drawing explanation
Fig. 1 is the stress-strain curve of the thermal reversion cross-linked polyurethane of different hard segment content in embodiment 2.
Fig. 2 is the alternating temperature of thermal reversion cross-linked polyurethane in embodiment 2 13c solid state nmr circulation experiment.
Fig. 3 is the stress-strain curve of the urethane that in embodiment 3 prepared by three kinds of different recoverying and utilizing methods.
Embodiment
Below in conjunction with embodiment, the invention will be further described, and the following stated embodiment will contribute to understanding the present invention, but can not limit protection scope of the present invention with this.
Embodiment 1: Thermally reversible covalent crosslinking-trihydroxy-DA affixture 4-(2,3-dihydroxypropyl)-6-hydroxyethyl-10-oxygen-4-nitrogen-three ring [5.2.1.0 2.6the synthesis in-8-alkene-3,5-diketone in the]-last of the ten Heavenly stems (TM)
In 1000ml single necked round bottom flask, add the maleic anhydride of 200g, the furans of 190g, after the ethyl acetate solution of 350ml, stirring at room temperature 24 hours, obtains white powdery solids TM-1 after reaction soln suction filtration, productive rate 90%. 1H NMR(400MHz，DMSO-d 6)：6.60(s，2H)，5.35(s，2H)，3.31(s，2H)ppm。
Take TM-1 powder 200g and be dissolved in 450ml dehydrated alcohol, join in the round-bottomed flask of 1000ml, after stirring, dropwise add and be dissolved with 112g 3-amino-1, the ethanol solution 120ml of 2-propylene glycol, is then warming up to 85 DEG C of backflows 8 hours, has reacted rear gained white precipitate, column chromatography for separation is purified and is obtained white solid TM-2, productive rate 70%. 1H NMR(400MHz，DMSO-d 6)：6.58(s，2H)，5.15(s，2H)，4.76(br，1H)，4.55(br，1H)，3.68(m，1H)，3.35(m，4H)，2.93(s，2H)ppm； 13C-NMR(400MHz，DMSO-d 6)：171.00，135.98，80.75，68.72，64.45，47.55，42.28ppm。
Being joined by the 220ml toluene solution being dissolved with 10gTM-2 is equipped with in churned mechanically there-necked flask; under the protection of nitrogen, 110 DEG C are refluxed 8 hours; react rear filtered while hot gained filtrate and to be kept in 0 DEG C of refrigerator 12 hours, obtain needle-like white crystallization TM-3, productive rate 50%. 1H NMR(400MHz，DMSO-d 6)：7.00(s，2H)，4.75(br，1H)，4.60(br，1H)，3.71(m，1H)，3.35(m，2H)ppm； 13C-NMR(400MHz，DMSO-d 6)：172.50，135.23，70.72，64.55，41.68ppm。
To in three mouthfuls of round-bottomed flasks of 1000ml, add the dried TM-3 of 25g, then add the toluene solution 450ml of 15g furfuryl alcohol, after then device is warming up to 85 DEG C, mechanical stirring 24h, in whole reaction process, device is among nitrogen atmosphere.After question response completes, use tetrahydrofuran (THF) washed product, then with anhydrous diethyl ether washing at least three times, after product chromatography, obtain target product TM. 1H NMR(400MHz，DMSO-d 6)：6.52(br，2H)，5.09(s，1H)，4.91(br，1H)，4.75(br，1H)，4.54(br，1H)，4.05(d，2H)，3.70(m，1H)，3.35(d，2H)，3.28(d，2H)，3.04(d，1H)，2.89(d，1H)ppm； 13C-NMR(400MHz，DMSO-d 6)：177.03，175.33，138.85，136.68，92.31，80.54，68.77，64.44，59.18，50.27，48.35，42.37ppm；mp 110℃。
Embodiment 2: a kind of preparation of thermal reversion cross-linked polyurethane
Under argon shield condition, take the polycaprolactone glycol (M strictly dewatered through 110 DEG C of vacuum n=2000g/mol) 50g and the liquid 4 that is kept in advance in 50 DEG C of baking ovens; 4 '-diphenylmethanediisocyanate 22g is in being equipped with in churned mechanically two mouthfuls of round-bottomed flasks; 65 DEG C of melting pre-polymerizations 2 hours; then after being warming up to 110 DEG C; add TM (the example 1 target product) 11.32g of thawing; rapid stirring, after 2 minutes, is poured in the mould of tetrafluoroethylene, 85 DEG C of slakings 3 hours in the baking oven of argon shield.Treat that oven temperature is again down to room temperature and just can be prepared the heat-curable urethane film that hard segment content is 40%, need in whole preparation flow to keep-NCO/-OH=1.05 (mol ratio).Adopt similar method to prepare thermal reversion cross-linked polyurethane that hard segment content is respectively 30% and 50%.
Fig. 1 is the stress-strain curve of the thermal reversion cross-linked polyurethane of three kinds of different hard segment contents of preparation.Show in figure, the increase that in urethane, hard segment content the works in coordination with content of crosslinking agent Young's modulus of material is had larger lifting, hard segment content be 50% urethane Young's modulus reach 132MPa, the rising of cross-linking density (comprising physical crosslinking and chemically crosslinked) simultaneously does not have larger impact to the breaking tenacity of material, still remain on about 40MPa, and the elongation at break of sample is still up to more than 330%.
Fig. 2 is the alternating temperature of thermal reversion cross-linked polyurethane 13c solid state nmr circulation experiment-comprise low temperature CPMAS tests and high temperature DPMAS tests.Show in figure, material is being heated in the process of 145 DEG C from 30 DEG C, cycloaddition thing wherein (is labeled as a, b at the peak at 49.7ppm, 81.4ppm and 90.1ppm place respectively and c) fades away, meanwhile, furan nucleus manifests at the peak at 142.8ppm and 150.4ppm place gradually at the peak at 110.4ppm place and maleimide ring, and illustrative material, when high temperature, DA reversed reaction occurs; When the temperature of material reduces again, the peak of low chemical shift place shows gradually again, and the peak of high chemical shift simultaneously gradually disappears again, and change now illustrates that DA reaction occurs once more when low temperature, has set up the crosslinking structure of polymer materials again.This is the molecular theory basis of the recyclable recycling of this type material.
Embodiment 3: the recycling of thermal reversion cross-linked polyurethane
The processing of high molecular material method that in this example, employing three kinds is general carries out recovery reprocessing to hard section containing the thermal reversion cross-linked polyurethane that content is 40%, is hot pressing formation process, injection moulding and solution film casting method respectively.Detailed operation steps is be divided into three parts after first polyurethane film prepared by body being cut into fragment, first part's fragment joins in the rectangular parallelepiped metal die of bottom for 40mm × 40mm, after applying certain pressure, be warming up to 135 DEG C of pressure-maintaining and heat-preservation 5min, the film sample for Elongation test can be prepared, same processing conditions, can process the sample of different shape by changing different moulds; Second section fragment joins in Thermo Scientific HAAKE Minijet II type injector, and after 145 DEG C of melting 5min, at the injected under pressure of 400bar in dumbbell shaped mould, the batten prepared can be directly used in Elongation test; The fragment of Part III is dissolved in (wt 20%) in organic solvent, again can dissolve, pour in Teflon mould after being heated to 130 DEG C in 15min, be placed into after in vacuum drying oven, 45 DEG C keep 24h, and 65 DEG C keep 24h, 85 DEG C keep 24h, to remove residual solvent completely.
Fig. 3 is these the three kinds stress-strain curves reclaiming the sample that process for subsequent treatment is prepared.Compared with the initial sample of hard segment content 40%, the sample mechanical property after recovery does not only decline and slightly raises on the contrary, and the different mechanical property of recovery working method on material also has impact simultaneously, can choose suitable method as required.
Should be noted that, the above-mentioned description to embodiment can understand and apply the invention for ease of those skilled in the art, person skilled in the art obviously can be easy to make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through creative work.Therefore, the invention is not restricted to embodiment here, those skilled in the art are according to announcement of the present invention, and the improvement made for the present invention and modification all should within protection scope of the present invention.

Claims (8)

1. a Thermally reversible covalent crosslinking, is characterized in that, has following general structure:
Wherein, R 1=CH 2cH 2oH or CH 2cH (OH) CH 2oH or CH (CH 2oH) CH 2oH;
R 2=R 3=H, CH 2oH, CH (CH 3) OH or CH 2cH (CH 3) OH;
R 4=H or CH 2oH; Wherein R 2, R 3, R 4can not be H simultaneously.
2. the synthetic method of Thermally reversible covalent crosslinking as claimed in claim 1, is characterized in that, comprise following four steps:
Step a: furans and maleic anhydride are dissolved in organic solvent, at room temperature reacts 24 hours, obtains product TM-1;
Step b: product TM-1 is dissolved in after in organic solvent, is slowly added dropwise to R 1-NH 2solution, after dropwising, reaction unit is warming up to 85 DEG C of backflows 8 hours gradually, obtains product TM-2 after gained precipitation suction filtration;
Step c: after product TM-2 is dissolved in organic solvent, under protection of inert gas, 110 DEG C are refluxed 8 hours, and then solution is placed 12 hours in 0 DEG C of refrigerator, and gained is precipitated as product TM-3;
Steps d: after product TM-3 is dissolved in organic solvent, under protection of inert gas, add the organic solvent solution of furan derivatives, reacts after 24 hours at 85 DEG C, can obtain the precipitation of target product TM.
3. synthetic method as claimed in claim 2, it is characterized in that, described furan derivatives is 2-furfuralcohol, 3-furfuralcohol, 1-(2-furyl) ethanol, 5-methyl-2-furfuralcohol, alpha-methyl-2-furans ethanol, the one in 2,5-FDM.
4. synthetic method as claimed in claim 2, is characterized in that, described R 1-NH 2for thanomin, 3-amino-1,2-PD, the one in 2-amino-1,3-propanediol.
5. synthetic method as claimed in claim 2, it is characterized in that, described organic solvent is ethyl acetate, tetrahydrofuran (THF), anhydrous diethyl ether, sherwood oil, toluene, methyl alcohol, ethanol, acetone, chloroform, dimethyl sulfoxide (DMSO), the one in dioxane or normal hexane.
6. synthetic method as claimed in claim 2, it is characterized in that, described rare gas element is nitrogen or argon gas.
7. synthetic method as claimed in claim 2, is characterized in that:
In described synthesis step a, the mass fraction of each reactant is: furans is 92.5-95.3 part, maleic anhydride is 100 parts, solvent is 150-200 part;
In described synthesis step b, the mass fraction of each reactant is: TM-1 is 100 parts, R 1-NH 2for 37.6-56 part, solvent are 200-300 part;
In described synthesis step c, the mass fraction of each reactant is: TM-2 is 5 parts, solvent is 100-150 part;
In described synthesis step d, the mass fraction of each reactant is: TM-3 is 100 parts, furan derivatives is 60-77 part, solvent is 1600-2000 part.
8. an application for Thermally reversible covalent crosslinking as claimed in claim 1, is characterized in that, as the linking agent preparing thermal reversion cross-linked polyurethane.
CN201510111733.7A 2015-03-13 2015-03-13 Thermally-reversible covalent crosslinking agent as well as synthesis method and application thereof Pending CN104804163A (en)

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CN105294936A (en) * 2015-10-19 2016-02-03 杭州龙勤新材料科技有限公司 Bi-functionality-degree acrylic ester cross-linking agent and application thereof to 3D printing
CN109749049A (en) * 2017-11-03 2019-05-14 北京化工大学 A kind of method that reversible chain extender prepares with it and prepares cross-linked polyurethane using it
CN109749049B (en) * 2017-11-03 2021-03-02 北京化工大学 Reversible chain extender, preparation thereof and method for preparing crosslinked polyurethane by using reversible chain extender
CN109957031A (en) * 2017-12-26 2019-07-02 北京化工大学 The reversible chain extender of cellulose fibre and its chain extender composition for preparing and include it
CN109957031B (en) * 2017-12-26 2020-12-22 北京化工大学 Cellulose fiber reversible chain extender, preparation thereof and chain extender composition containing same
CN108586700A (en) * 2018-05-15 2018-09-28 浙江华峰热塑性聚氨酯有限公司 non yellowing can self-healing thermoplastic polyurethane elastomer and preparation method thereof
US20200308365A1 (en) * 2019-03-26 2020-10-01 United States Of America As Represented By The Administrator Of Nasa Recycle Feedstocks for On-Demand Article Manufacturing
US11649337B2 (en) * 2019-03-26 2023-05-16 United States Of America As Represented By The Administrator Of Nasa Recycle feedstocks for on-demand article manufacturing
CN111777824A (en) * 2019-04-03 2020-10-16 北京创源市政建设工程有限公司 Windable PVC lining pipe, preparation thereof and trenchless pipeline repairing process using same
CN111777824B (en) * 2019-04-03 2022-03-29 北京创源市政建设工程有限公司 Windable PVC lining pipe, preparation thereof and trenchless pipeline repairing process using same

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Application publication date: 20150729