CN110105532A - Thermoplasticity selfreparing polyurethane resin and preparation method thereof for 3D printing composite material - Google Patents
Thermoplasticity selfreparing polyurethane resin and preparation method thereof for 3D printing composite material Download PDFInfo
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- CN110105532A CN110105532A CN201910368606.3A CN201910368606A CN110105532A CN 110105532 A CN110105532 A CN 110105532A CN 201910368606 A CN201910368606 A CN 201910368606A CN 110105532 A CN110105532 A CN 110105532A
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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
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
- C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
- C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
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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
- C08G18/28—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
- C08G18/428—Lactides
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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
- C08G18/28—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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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
Abstract
The thermoplasticity selfreparing polyurethane resin and preparation method thereof that the invention discloses a kind of for 3D printing composite material, the resin includes that following raw material in parts by mass is made: macromolecule dihydric alcohol 100, diisocyanate 10 ~ 25, small molecule trihydroxylic alcohol 1 ~ 8, bis- (2- ethoxy) disulfides 2 ~ 6, catalyst 0.1 ~ 2.02.The resin is using macromolecule dihydric alcohol as polyurethane system molecule soft segment, using curing agent diisocyanate, crosslinking agent small molecule trihydroxylic alcohol as molecule hard section, bis- (2- ethoxy) disulfides containing cystine linkage are introduced as chain extender, design synthesizes the block polymers of polyurethane structure with hydroxy-end capped suspended chain.High resiliency is showed at normal temperature；Under heating status, material is changed into viscous state by elastomeric state, can carry out material selfreparing and reshaping, is greatly facilitated thermoplastic polyurethane resin and promotes and applies in the increasing material manufacturing of high solids content composite material.
Description
Technical field
The present invention relates to 3D printing field, specially a kind of thermoplasticity selfreparing polyurethane for 3D printing composite material
Resin and preparation method thereof.
Background technique
Composite material is by two kinds and two or more materials of different nature, by the method for physics or chemistry, macro
See the material that composition on (microcosmic) has new capability.Reisn base material determines the comprehensive performance of composite material, is composite wood
Expect the key of research and development.Thermoplastic polymer elastomer is by the block polymer structure with different coherent conditions or crystal property
At when temperature is higher than its melting temperature, polymer softening melting is viscous state；It is hard when temperature is lower than its melting temperature
Section forms the glassy state or crystalline state of microphase-separated, plays the role of physical crosslinking, and assign polymer thermal reversibility.Thermoplasticity
Polymer elastomer has the physical mechanical property of vulcanized rubber and the processing performance of thermoplastic, has reduction waste
(Reduce), make the best use of everything (Reuse), recycle use (Recycle) 3R characteristic, thus in many application fields instead of
Thermo-setting elastomer.Currently, but failing to introduce the function with self-repair function in most of thermoplastic polyurethane molecular structure
Group, affects making for thermoplastic polyurethane material at the problem of leading to material apparent mass, safeguard function, mechanical properties decrease
With service life, apparent mass and product durability.Intrinsic self-repair material mainly passes through D-A key, cystine linkage, hydrogen bond, hydrophobic work
With realizations fast and efficiently selfreparings such as, pi-pi accumulation, ionization and host-guest interactions, without harsh reaction condition and
Use cumbersome coating technology.Wherein, cystine linkage type self-healing polymers material is anti-based on the reversible exchange of cystine linkage-sulfydryl
Answer, can carry out at room temperature, and stimulated without other external conditions, at the same have self-repair efficiency it is high, can be repeated
Advantage.
Summary of the invention
The present invention provides a kind of thermoplasticity selfreparing polyurethane resin and preparation method thereof for 3D printing composite material,
The resin shows high resiliency at normal temperature；Under heating status, material is changed into viscous state by elastomeric state, can carry out material selfreparing
And reshaping, it is greatly facilitated thermoplastic polyurethane resin and is promoted and applied in the increasing material manufacturing of high solids content composite material.
Concrete scheme of the invention is to provide thermoplasticity selfreparing polyurethane resin, molecular structural formula are as follows:
Wherein A:
R1Residual groups after losing three hydroxyls for small molecule trihydroxylic alcohol,
R2Residual groups after losing two isocyanate group for diisocyanate,
R3Residual groups after losing two hydroxyls for macromolecule dihydric alcohol.
The invention further relates to the method for preparing the thermoplasticity selfreparing polyurethane resin, which includes in parts by mass
Following raw material be made:
The following steps are included:
1) diisocyanate curing agent and catalyst is added into macromolecule dihydric alcohol under nitrogen atmosphere, it is warming up to 50~
80 DEG C of 3~6h of reaction, obtain polyurethane prepolymer；
2) will be bis- in (2- ethoxy) disulfide dissolution solvent, it is pre- that it is added to above-mentioned polyurethane together with small molecule trihydroxylic alcohol
In polymers, 50~60 DEG C of heat preservation is simultaneously stirred evenly, in a mold moulding by casting, is solidified after being vacuum-evacuated at 20~60 DEG C, is obtained
To thermoplasticity selfreparing polyurethane resin.
Further, the macromolecule dihydric alcohol is end hydroxy butadiene, hydroxyl telechelic polyester dihydric alcohol, terminal hydroxy group gather
Ether dihydric alcohol, terminal hydroxy group long chain alkane dihydric alcohol glycidyl azide polymer, terminal hydroxy group ethylene oxide tetrahydrofuran copolyether, end
Hydroxyl polylactic acid it is one or more.
Further, the diisocyanate is isophorone diisocyanate, hexamethylene diisocyanate, dimerization
Fatty acid diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, dicyclohexyl methyl hydride diisocyanate,
One of 3,3 '-dimethyl -4,4 '-biphenyl diisocyanate is a variety of.
Further, the hydroxy acrylate be hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl,
Hydroxyethyl methacrylate, hydroxy propyl methacrylate, trimethylolpropane diacrylate, pentaerythritol diacrylate,
One of pentaerythritol triacrylate, 1,6 hexanediol diacrylate are a variety of.
Further, the small molecule trihydroxylic alcohol is glycerine, triethanolamine, trimethylolpropane, 1,2,4- fourths three
One of alcohol, triisopropanolamine are a variety of.
For polyurethane resin different parameters requirement, such as fusing point, tensile strength, degradable speed, glass transition temperature,
Energy water equality introduces different macromolecule dihydric alcohols, diisocyanate, small molecule trihydroxylic alcohol, the reaction speed controlled as needed
Spend selecting catalyst.
Further, the catalyst is triphenyl bismuth, three (ethoxyl phenenyl) bismuths, ferric acetyl acetonade, tin dilaurate two
One of butyl tin, triphenyltin chloride are a variety of.
Further, in step 2), 50~70 DEG C keep the temperature 30~90min of stirring under lower 300~600r/min revolving speed, then
Moulding by casting in a mold.
Further, mold is polytetrafluoroethylene (PTFE) material.
The invention further relates to application of the thermoplasticity selfreparing polyurethane resin in 3D printing composite material.
The invention has the following advantages:
1, the present invention using macromolecule dihydric alcohol as polyurethane system molecule soft segment, using curing agent diisocyanate,
Crosslinking agent small molecule trihydroxylic alcohol introduces bis- (2- ethoxy) disulfides containing cystine linkage as chain extender as molecule hard section, if
Meter synthesizes the block polymers of polyurethane structure with hydroxy-end capped suspended chain, material soft and hard segments moiety aggregation at normal temperature
At orderly class crystal structure, soft segment part then keeps unordered coiled structure, and false cross-linked network structure is integrally presented in material, performance
High resiliency；And under heating status, the orderly class crystalline substance of hard section moiety aggregation is melted, and with soft segment partially compatible, material is by high-elastic
State is changed into viscous state, can carry out material selfreparing and reshaping, have reduce waste (Reduce), make the best use of everything (Reuse),
Recycling uses the 3R characteristic of (Recycle), can be greatly facilitated thermoplastic polyurethane resin in the increasing material of high solids content composite material
It is promoted and applied in manufacture.
2, the present invention uses substep preparation method, first obtains polyurethane prepolymer, then with bis- (2- ethoxy) disulfides into
Row polymerization obtains selfreparing polyurethane, reviews one's lessons by oneself compared to what the selfreparing polyurethane first obtained carried out that cystine linkage heat cross-linking obtains again
The self-repair efficiency of multiple polyurethane, the selfreparing polyurethane that the present invention obtains is high, and mechanical property is more excellent.In addition, passing through control
The proportion of the molecules hard sections and macromolecule dihydric alcohol molecule soft segment such as curing agent diisocyanate, crosslinking agent small molecule trihydroxylic alcohol, can
So that the selfreparing polyurethane mechanical property that the present invention obtains is more excellent, and melting temperature is higher than selfreparing temperature, convenient for not breaking
Under the premise of bad polyurethane material form, selfreparing is carried out；And the obtained polyurethane material of preparation method provided by the invention
Molecular weight is controllable, and molecular weight distribution is relatively narrow, and in 1.1~1.3 ranges, and mechanical property is more excellent, tensile strength be 3.28~
35.8MPa, elongation at break are 120~950%, and self-repair efficiency is higher, 84.5% or more；65~255 DEG C of fusing point, glass
Change temperature -88~-50 DEG C, 7~96 Shao A of hardness.
Specific embodiment
Below with reference to embodiment, the present invention is furture elucidated.
Embodiment 1:
Thermoplasticity selfreparing polyurethane resin:
1) synthesis of polyurethane prepolymer: 200g end hydroxy butadiene is added in the three-necked flask equipped with stirrer,
The 42.9g dicyclohexyl methyl hydride diisocyanate measured and 0.4g tri- (ethoxyl phenenyl) bismuth are added under nitrogen atmosphere, rises
Stop after temperature to 50 DEG C of reaction 6h, obtains polyurethane prepolymer；
2) bis- (2- ethoxy) disulfides of 4.8g first the synthesis of thermoplasticity selfreparing polyurethane resin: are dissolved in 10ml tetra-
It in hydrogen furans, is added to together with 2.5g glycerine in the three-necked flask where above-mentioned polyurethane prepolymer, under 60 DEG C of heat preservations
90min is stirred under 300r/min revolving speed, is cast in Teflon mould, in 60 DEG C of curing moldings after being vacuum-evacuated, is obtained
To thermoplasticity selfreparing polyurethane resin.
The thermoplasticity selfreparing polyurethane resin has the following performance:
Embodiment 2:
Thermoplasticity selfreparing polyurethane resin:
1) synthesis of polyurethane prepolymer: 50g terminal hydroxy group long chain alkane dihydric alcohol glycidyl azide polymer is added and is filled
Have in the three-necked flask of stirrer, the 12g diisocyanate curing agent and 0.4g second measured is added under nitrogen atmosphere
Acyl acetone iron stops after being warming up to 60 DEG C of reaction 4h, obtains polyurethane prepolymer；
2) bis- (2- ethoxy) disulfides of 1.24g first the synthesis of thermoplasticity selfreparing polyurethane resin: are dissolved in 5ml tetra-
It in hydrogen furans, is added to together with 0.54g triethanolamine in the three-necked flask where above-mentioned polyurethane prepolymer, under 60 DEG C of heat preservations
Stir 30min under 600r/min revolving speed, be cast in Teflon mould, after being vacuum-evacuated at 60 DEG C curing molding,
Obtain thermoplasticity selfreparing polyurethane resin.
The thermoplasticity selfreparing polyurethane resin has the following performance:
Embodiment 3:
Thermoplasticity selfreparing polyurethane resin:
1) synthesis of polyurethane prepolymer: 1000g terminal hydroxy group ethylene oxide tetrahydrofuran copolyether is added equipped with stirring
In the three-necked flask of son, the 213.9g methyl diphenylene diisocyanate measured and 3.4g chlorination three are added under nitrogen atmosphere
Phenyltin stops after being warming up to 80 DEG C of reaction 3h, obtains polyurethane prepolymer；
2) bis- (2- ethoxy) disulfides of 24.8g first the synthesis of thermoplasticity selfreparing polyurethane resin: are dissolved in 100ml
In tetrahydrofuran, it is added to together with 12.5g trimethylolpropane in the three-necked flask where above-mentioned polyurethane prepolymer, 50 DEG C
It keeps the temperature and stirs 60min under lower 300r/min revolving speed, be cast in Teflon mould, solidify at 60 DEG C after being vacuum-evacuated
Molding, obtains thermoplasticity selfreparing polyurethane resin.
The thermoplasticity selfreparing polyurethane resin has the following performance:
Embodiment 4:
Thermoplasticity selfreparing polyurethane resin:
1) synthesis of polyurethane prepolymer: 2000g hydroxyl-terminated polylactic acid is added in the three-necked flask equipped with stirrer,
The 478g dimer (fatty acid) yl diisocyanate and 4.8g triphenyl bismuth measured is added under nitrogen atmosphere, is warming up to 50 DEG C of reaction 3h
After stop, obtaining polyurethane prepolymer；
2) bis- (2- ethoxy) disulfides of 49.3g first the synthesis of thermoplasticity selfreparing polyurethane resin: are dissolved in 500ml
In tetrahydrofuran, and 32g1,2,4- butantriols are added to together in the three-necked flask where above-mentioned polyurethane prepolymer, heat preservation 70
It DEG C keeps the temperature and to stir 30min under lower 600r/min revolving speed, be cast in Teflon mould, it is solid at 60 DEG C after being vacuum-evacuated
Chemical conversion type obtains thermoplasticity selfreparing polyurethane resin.
The thermoplasticity selfreparing polyurethane resin has the following performance:
Claims (10)
1. thermoplasticity selfreparing polyurethane resin, which is characterized in that molecular structural formula are as follows:
Wherein A:
R1Residual groups after losing three hydroxyls for small molecule trihydroxylic alcohol,
R2Residual groups after losing two isocyanate group for diisocyanate,
R3Residual groups after losing two hydroxyls for macromolecule dihydric alcohol.
2. the method for preparing thermoplasticity selfreparing polyurethane resin described in claim 1, which is characterized in that the resin includes pressing matter
The following raw material of amount part meter is made:
Specifically includes the following steps:
1) diisocyanate curing agent and catalyst is added into macromolecule dihydric alcohol under nitrogen atmosphere, is warming up to 50~80 DEG C
3~6h is reacted, polyurethane prepolymer is obtained；
2) will be bis- in (2- ethoxy) disulfide dissolution solvent, it is added to above-mentioned polyurethane prepolymer together with small molecule trihydroxylic alcohol
In, 50~60 DEG C of heat preservation simultaneously quickly stirs evenly, in a mold moulding by casting, solidifies after being vacuum-evacuated at 20~60 DEG C, obtains
To thermoplasticity selfreparing polyurethane resin.
3. according to the method described in claim 2, it is characterized by: the macromolecule dihydric alcohol be end hydroxy butadiene,
Hydroxyl telechelic polyester dihydric alcohol, polyether glycol, terminal hydroxy group long chain alkane dihydric alcohol glycidyl azide polymer, terminal hydroxy group
Ethylene oxide tetrahydrofuran copolyether, hydroxyl-terminated polylactic acid it is one or more.
4. according to the method described in claim 2, it is characterized by: the diisocyanate is isophorone diisocyanate
Ester, hexamethylene diisocyanate, dimer (fatty acid) yl diisocyanate, toluene di-isocyanate(TDI), diphenylmethane diisocyanate
One of ester, dicyclohexyl methyl hydride diisocyanate, 3,3 '-dimethyl -4,4 '-biphenyl diisocyanate are a variety of.
5. according to the method described in claim 2, it is characterized by: the hydroxy acrylate is hydroxy-ethyl acrylate, third
Olefin(e) acid hydroxypropyl acrylate, hy-droxybutyl, hydroxyethyl methacrylate, hydroxy propyl methacrylate, two propylene of trimethylolpropane
One of acid esters, pentaerythritol diacrylate, pentaerythritol triacrylate, 1,6 hexanediol diacrylate are more
Kind.
6. according to the method described in claim 2, it is characterized by: the small molecule trihydroxylic alcohol be glycerine, triethanolamine,
One of trimethylolpropane, 1,2,4- butantriol, triisopropanolamine are a variety of.
7. according to the method described in claim 2, it is characterized by: the catalyst is triphenyl bismuth, three (ethoxyl phenenyls)
One of bismuth, ferric acetyl acetonade, dibutyl tin dilaurate, triphenyltin chloride are a variety of.
8. according to the method described in claim 2, it is characterized by: 50~60 DEG C keep the temperature lower 300~600r/min in step 2)
30~90min is quickly stirred under revolving speed, then moulding by casting in a mold.
9. according to the method described in claim 2, it is characterized by: the mold is polytetrafluoroethylene (PTFE) material.
10. application of the thermoplasticity selfreparing polyurethane resin in 3D printing composite material described in claim 1.
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Cited By (10)
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|---|---|---|---|---|
| CN110591542A (en) * | 2019-08-28 | 2019-12-20 | 山东大学 | Disulfide bond and hydrogen bond containing dual self-repairing polyurethane coating for invisible car cover and preparation method thereof |
| CN112062926A (en) * | 2020-09-16 | 2020-12-11 | 北京理工大学 | Cross-linking type fusible casting energetic polymer adhesive material |
| CN112225860A (en) * | 2020-10-12 | 2021-01-15 | 美瑞新材料股份有限公司 | High-hardness thermoplastic polyurethane resin capable of being softened for multiple times at low temperature and application thereof in profile molding |
| CN112574375A (en) * | 2019-09-30 | 2021-03-30 | 中国科学院宁波材料技术与工程研究所 | Self-healing hydrophobic polyurethane and preparation method and application thereof |
| CN112646535A (en) * | 2020-12-23 | 2021-04-13 | 广东龙马新材料科技有限公司 | High-strength environment-friendly wood board adhesive and preparation method thereof |
| CN113201215A (en) * | 2020-12-24 | 2021-08-03 | 江苏集萃先进高分子材料研究所有限公司 | Selective laser sintering self-repairing polyurethane powder material and preparation method thereof |
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| WO2023185076A1 (en) * | 2022-03-31 | 2023-10-05 | 深圳先进技术研究院 | Intrinsic self-repairing thermally conductive macromolecular polymer based on lipoic acid or/and derivative thereof, method for preparing same, and use thereof |
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| CN112646535B (en) * | 2020-12-23 | 2022-07-12 | 广东龙马新材料科技有限公司 | High-strength environment-friendly wood board adhesive and preparation method thereof |
| CN113201215A (en) * | 2020-12-24 | 2021-08-03 | 江苏集萃先进高分子材料研究所有限公司 | Selective laser sintering self-repairing polyurethane powder material and preparation method thereof |
| CN113201215B (en) * | 2020-12-24 | 2022-09-16 | 江苏集萃先进高分子材料研究所有限公司 | Selective laser sintering self-repairing polyurethane powder material and preparation method thereof |
| WO2023185076A1 (en) * | 2022-03-31 | 2023-10-05 | 深圳先进技术研究院 | Intrinsic self-repairing thermally conductive macromolecular polymer based on lipoic acid or/and derivative thereof, method for preparing same, and use thereof |
| CN115181243A (en) * | 2022-06-01 | 2022-10-14 | 西南科技大学 | Self-repairing detachable butadiene-hydroxy glue cured product and compound thereof |
| CN115651514A (en) * | 2022-09-28 | 2023-01-31 | 中国人民解放军陆军工程大学 | Infrared and laser compatible stealth coating with self-repairing function and good mechanical property |
| CN115746618A (en) * | 2022-11-23 | 2023-03-07 | 黎明化工研究设计院有限责任公司 | Internal release agent, self-releasing double-component self-repairing transparent polyurethane coating and preparation method thereof |
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