CN108586693A - It is a kind of with triple dynamic keys can process again and the shape-memory material of solid plastics - Google Patents
It is a kind of with triple dynamic keys can process again and the shape-memory material of solid plastics Download PDFInfo
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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
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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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
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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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
- C08G2230/00—Compositions for preparing biodegradable polymers
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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
- C08G2280/00—Compositions for creating shape memory
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- Polymers & Plastics (AREA)
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Abstract
The invention belongs to shape memory material technology fields, and in particular to it is a kind of with triple dynamic keys can process again and the shape-memory material of solid plastics.For the heavy poor processability of covalent cross-linking type shape-memory material in the prior art, the defect that the mechanical performance of material substantially reduces process again after, the technical scheme is that：The shape memory high molecule material is the shape-memory material of covalent cross-linking, includes three kinds of ester group, urea groups and carbamate groups dynamic keys in the cross-linked network of shape memory high molecule.The shape memory high molecule material can be selected following raw materials and prepare：50 90 parts of polycaprolactone；0.1 50 parts of monomer with the amido that is obstructed；0.1 30 parts of trifunctional group cross-linking agent；0.1 5 parts of catalyst；10 300 parts of solvent.The present invention is suitable for shape-memory material.
Description
Technical field
The invention belongs to shape memory material technology fields, and in particular to it is a kind of with triple dynamic keys can process again and
The shape-memory material of solid plastics.
Background technology
As a kind of intellectual material, shape-memory material can fix temporary shapes, and when by environmental stimuli such as heat,
Moisture, pH, light, electricity etc. can be restored to their original shape.Due to shape-memory material in our life and industrially
There is huge potential application, therefore it receives the extensive concern of people.
Currently, thermal response shape memory high molecule material is a kind of shape-memory material of most study, by adjustingization
Learn component, it is easy to adjust its crystallinity, hot property and shape-memory properties in a wider range, some shapes note
Recalling material also has biocompatibility and biological degradability, and therefore, shape-memory material has very high answer in biomedicine field
With as fabric, intelligent medical equipment and organizational project can be breathed for Minimally Invasive Surgery, orthopaedic srugery, intelligence.In shape memory material
In material, the shape-memory material of covalent cross-linking has making for very high shape recovery rate, fast-response, big recovery stress and length
With the service life, these features all meet the requirement of biomedicine field very much.However, compared with thermoplasticity shape-memory material, altogether
The crosslinked shape-memory material of valence cannot be processed again, and its original shape cannot change, and therefore, it is difficult to meet clinically
Application.
In conclusion pair excipient and the research of thermoset shape memory material that can be processed can become current research again again
Hot spot.Can be again in the shape-memory material of excipient, by solid plastics, this be new first by 105037702 B of Chinese patent CN
Concept be introduced into shape-memory material, and this kind of shape-memory material is named as hot adaptive shape-memory material.Due to
The exchange of dynamic covalent bond, solid plastics enable shape-memory material to remold its original shape, and need not be by
Mold can obtain highly complex original shape, but their shape-memory material can only realize assigning again for original shape
Type can not achieve the processing again of shape-memory material.
In view of the thermoset shape memory material that can be processed again, the dynamic covalent bond with low-activation energy is introduced into polymerization
Object network come realize thermoset shape memory material processing again and recycling be a good method.Although weight processability and
Solid plastics both are from dynamic covalent bond, but the two is combined to the preferable weight processability of realization and solid plastics well
Relevant report it is seldom, main difficult point be the temperature and solid plastics processed again deformation temperature needs be significantly higher than
The transition temperature of shape memory, otherwise, in shape memory deformation process, network structure is in the transition temperature less than shape memory
When by dynamic key exchange can lead to certain stress relaxation, to influence or weaken shape-memory properties.It is asked to solve this
Topic, needs a variety of dynamic keys with different activation temperatures being introduced into a network.Document (Z.Z.Fang, N.Zheng,
Q.Zhao, T.Xie, ACS Appl.Mater.Interfaces 2017,9,22077) urea bond that will be obstructed and urethane bond
It is introduced into a polymer network, the combination of processing and plasticity again is obtained, since the dynamic exchange for urea bond of being obstructed is in room temperature
Under can carry out, in order to obtain preferable shape-memory properties, the content for urea bond of being obstructed is limited in a rather low level,
But which results in poor heavy processabilities, for example, process again after, stress is only returned to the 45% of raw sample.
Invention content
For the heavy poor processability of covalent cross-linking type shape-memory material in the prior art, the machinery of material process again after
The defect that performance substantially reduces, the present invention provides a kind of can process again with triple dynamic keys and the shape of solid plastics notes
Recall material, its object is to：Pass through triple dynamic keys so that shape-memory material has preferable solid plastics, original shape
Excipient ability again, and shape-memory material still has good mechanical performance after processing again.
The technical solution adopted by the present invention is as follows：
It is a kind of with triple dynamic keys can process again and the shape-memory material of solid plastics, the shape memory high score
Sub- material is the shape-memory material of covalent cross-linking, includes ester group, urea groups and amino in the cross-linked network of shape memory high molecule
Three kinds of dynamic keys of formic acid ester group.
After the technical solution, shape memory high molecule material is made by the dynamic exchange of three kinds of dynamic keys while being had
There are weight processability and solid plastics well.Triple dynamic key exchange mechanisms are as follows：
R1、R2、R3And R4It is the strand of different piece in shape memory high molecule.Urea bond of being wherein obstructed has preferable
Dynamic exchange rate is conducive to the heavy processability for improving material entirety, but at room temperature due to the dynamic exchange for urea bond of being obstructed
It can carry out, in order to obtain preferable shape-memory properties, the content for urea bond of being obstructed is limited in a rather low level, but
It is which results in poor heavy processabilities.And a large amount of ester group is also added into the technical program, in macromolecule network, adding again
Ester exchange reaction can occur for ester group during work so that the strand being broken in weight process can be repaired, and process again
The strain of shape memory high molecule material and tensile strength can be restored well afterwards.
Preferably, shape memory high molecule is the material of polyester, polyureas and urethane crosslinks.
Preferably, the shape memory high molecule material with triple dynamic keys is made of the raw material of following parts by weight：
50-90 parts of polycaprolactone；
0.1-50 parts of monomer with the amido that is obstructed；
0.1-30 parts of trifunctional group cross-linking agent；
0.1-5 parts of catalyst；
10-300 parts of solvent.
After the preferred embodiment, the polycaprolactone of selection is easy to the shape memory high molecule material degraded, thus made
Also there is biodegradability.In addition polycaprolactone has higher crystallinity, is spread by melting, chain and winding can realize heat
It repairs and reversible adherency.The chemical structural formula of shape memory high molecule in this preferred embodiment is as follows：
It is further preferred that the polycaprolactone is the oligomer of weight average molecular weight 1000-3000.It should be preferably so that ester group
It is more uniform with the mixing of other groups so that the performance inside shape memory high molecule material is more uniform.
It is further preferred that the monomer with the amido that is obstructed is tertiary butyl ethanol amine or N, in N'- di-t-butyl ethylenediamines
One or two kinds of combinations, can be adjusted according to the requirement to material overall performance.
It is further preferred that trifunctional group cross-linking agent is (2,4,6- trioxy- triazines -1,3,5 (2H, 4H, 6H)-three base)
Three (hexa-methylene) isocyanates.In addition to crosslinked effect, another effect is and polycaprolactone shape trifunctional group cross-linking agent
Urea groups is formed at carbamate groups and with the monomer with the amido that is obstructed.
It is further preferred that catalyst is one or both of dibutyl tin laurate or stannous iso caprylate.
A kind of can process again with triple dynamic keys and the preparation method of the shape-memory material of solid plastics, including such as
Lower step：To be used to form ester group, the polymerized monomer raw material of three kinds of dynamic keys of urea groups and carbamate groups and catalyst by than
Example is added in solvent, and stirring and dissolving obtains solution at room temperature；Then solution is injected in reaction mold, heating reaction, after demoulding
Drying at room temperature obtains shape memory high molecule material.
The preparation method can realize thermosetting by adjusting temperature, catalyst content, content of monomer and dynamic key class etc.
Property shape memory high molecule material original shape complication, again excipient and weight processing performance etc., be a kind of to obtain excellent shape
The effective ways of shape memory performance and the thermoset shape memory high molecular material of weight processing performance.
In conclusion by adopting the above-described technical solution, the beneficial effects of the invention are as follows：
1. shape memory high molecule material while having to process well by the dynamic exchange of three kinds of dynamic keys again
Property and solid plastics, be it is a kind of can process again and original shape can excipient again thermoset shape memory high molecular material.It will cut
Fragmented material is put into mold, under certain temperature and pressure, is exchanged by triple dynamic keys, can be realized thermosetting property
The processing again of shape-memory material.
2. by the way that ester group is added, shape is remembered after overcoming the processing again brought in the prior art to the limitation of urea groups content
It is difficult the problem of being restored to previous level to recall the performances such as strain and the tensile strength of high molecular material.
3. the polycaprolactone selected, which is easy to the shape memory high molecule material degraded, thus made, also has biodegradable
Property.In addition polycaprolactone has higher crystallinity, is spread by melting, chain and winding can realize that hot repair is multiple and reversible and glue
It is attached.
4. selecting the oligomer of polycaprolactone so that the mixing of ester group and other groups is more uniform so that shape memory
Performance inside high molecular material is more uniform.
5. the monomer with the amido that is obstructed of Different Dynamic key exchange rate is selected to make finally formed urea groups with not
Same dynamic property, can be adjusted according to the requirement to material overall performance.
6. trifunctional group cross-linking agent is in addition to crosslinked effect, another effect is to form carbamate with polycaprolactone
Base and with the amido that is obstructed monomer formed urea groups.
7. the preparation method in the present invention can be by adjusting temperature, catalyst content, content of monomer and dynamic key class etc.
It realizes complication, again excipient and weight processing performance etc. of thermoset shape memory high molecular material original shape, is a kind of
Obtain the effective ways of excellent shape memory performance and the thermoset shape memory high molecular material of weight processing performance.
Specific implementation mode
All features disclosed in this specification or disclosed all methods or in the process the step of, in addition to mutually exclusive
Feature and/or step other than, can combine in any way.
A kind of shape memory high molecule material with triple dynamic keys, the shape memory high molecule material are covalently to hand over
The shape-memory material of connection, it is dynamic comprising three kinds of ester group, urea groups and carbamate groups in the cross-linked network of shape memory high molecule
State key.
Preferably, shape memory high molecule is the material of polyester, polyureas and urethane crosslinks.
Preferably, it is made of the raw material of following parts by weight：
50-90 parts of polycaprolactone；
0.1-50 parts of monomer with the amido that is obstructed；
0.1-30 parts of trifunctional group cross-linking agent；
0.1-5 parts of catalyst；
10-300 parts of solvent.
It is further preferred that polycaprolactone is the oligomer of weight average molecular weight 1000-3000.
It is further preferred that the monomer with the amido that is obstructed is tertiary butyl ethanol amine or N, in N'- di-t-butyl ethylenediamines
One or two kinds of combinations.
It is further preferred that trifunctional group cross-linking agent is (2,4,6- trioxy- triazines -1,3,5 (2H, 4H, 6H)-three base)
Three (hexa-methylene) isocyanates.
It is further preferred that catalyst is the group of one or both of dibutyl tin laurate or stannous iso caprylate
It closes.
A kind of preparation method of the shape memory high molecule material with triple dynamic keys, includes the following steps：It will be used for
Ester group, the polymerized monomer raw material of three kinds of dynamic keys of urea groups and carbamate groups and catalyst by proportion is formed to be added in solvent,
Stirring and dissolving obtains solution at room temperature；Then solution is injected in reaction mold, heating reaction, room temperature drying to obtain after demoulding
Shape memory high molecule material.
Further illustrate is made to technical scheme of the present invention below：
Embodiment 1
Preparing raw material is：
Polycaprolactone (Mn=2000) 6g；
N, N'- di-t-butyl ethylenediamine 0.1034g；
(- three base of 2,4,6- trioxy-s triazine -1,3,5 (2H, 4H, 6H)) three (hexa-methylene) isocyanates 0.8604g；
Catalyst：Dibutyl tin laurate 0.03g, stannous iso caprylate 0.03g；
Solvent：Dichloromethane 15g.
Preparation method is：Polycaprolactone 6g and N, N'- di-t-butyl ethylenediamine 0.1034g are mixed in 15g dichloromethane
Uniformly, (2,4,6- trioxy- triazines -1,3,5 (2H, 4H, 6H)-three base) three (hexa-methylene) isocyanates are then added
0.8604g, dibutyl tin laurate 0.03g, stannous iso caprylate 0.03g, are poured into mold after mixing, and 25 degrees Celsius solid
Change 24 hours, 80 degrees Celsius are dried in vacuum overnight removing solvent, demoulding.
Some performance indicators of product：
After processing 15min again at 170 degrees Celsius of 10MPa, strain is restored to the 74.6% of primary sample, and stress recovery arrives
The 80.5% of primary sample.Compared with the data stress recovery 45% in document, the present embodiment process again after stress recovery energy
Power greatly promotes.
Comparative example 1
Preparing raw material is：
Polyethylene glycol (Mn=2000) 6g,
N, N'- di-t-butyl ethylenediamine 0.1034g,
(2,4,6- trioxy- triazines -1,3,5 (2H, 4H, 6H)-three base) three (hexa-methylene) isocyanates 0.8604g,
Catalyst：Dibutyl tin laurate 0.03g, stannous iso caprylate 0.03g,
Solvent：Dichloromethane 15g.
Preparation method is：Polyethylene glycol 6g and N, N'- di-t-butyl ethylenediamine 0.1034g are mixed in 15g dichloromethane
It closes uniformly, (2,4,6- trioxy- triazines -1,3,5 (2H, 4H, 6H)-three base) three (hexa-methylene) isocyanates is then added
0.8604g, dibutyl tin laurate 0.03g, stannous iso caprylate 0.03g, are poured into mold after mixing, and 25 degrees Celsius solid
Change 24 hours, 80 degrees Celsius are dried in vacuum overnight removing solvent, demoulding.
Some performance indicators of product：
After processing 15min again at 170 degrees Celsius of 10MPa, strain is restored to the 39% of primary sample, stress recovery to original
The 51.6% of beginning sample.
Comparative example 2
Preparing raw material is：
Polycaprolactone (Mn=2000) 6g,
N, N'- diethyl ethylenediamine 0.0697g,
(2,4,6- trioxy- triazines -1,3,5 (2H, 4H, 6H)-three base) three (hexa-methylene) isocyanates 0.8604g,
Catalyst：Dibutyl tin laurate 0.03g, stannous iso caprylate 0.03g,
Solvent：Dichloromethane 15g,
Preparation method is：Polycaprolactone 6g and N, N'- diethyl ethylenediamines 0.0697g are mixed in 15g dichloromethane
Uniformly, (2,4,6- trioxy- triazines -1,3,5 (2H, 4H, 6H)-three base) three (hexa-methylene) isocyanates are then added
0.8604g, dibutyl tin laurate 0.03g, stannous iso caprylate 0.03g, are poured into mold after mixing, and 25 degrees Celsius solid
Change 24 hours, 80 degrees Celsius are dried in vacuum overnight removing solvent, demoulding.
Some performance indicators of product：
After processing 15min again at 170 degrees Celsius of 10MPa, strain is restored to the 35.8% of primary sample, and stress recovery arrives
The 58.3% of primary sample.
Comparative example 3
Preparing raw material is：
Polyethylene glycol (Mn=2000) 6g,
N, N'- diethyl ethylenediamine 0.0697g,
(2,4,6- trioxy- triazines -1,3,5 (2H, 4H, 6H)-three base) three (hexa-methylene) isocyanates 0.8604g,
Catalyst：Dibutyl tin laurate 0.03g, stannous iso caprylate 0.03g,
Solvent：Dichloromethane 15g.
Preparation method is：Polyethylene glycol 6g and N, N'- diethyl ethylenediamines 0.0697g are mixed in 15g dichloromethane
Uniformly, (2,4,6- trioxy- triazines -1,3,5 (2H, 4H, 6H)-three base) three (hexa-methylene) isocyanates are then added
0.8604g, dibutyl tin laurate 0.03g, stannous iso caprylate 0.03g, are poured into mold after mixing, and 25 degrees Celsius solid
Change 24 hours, 80 degrees Celsius are dried in vacuum overnight removing solvent, demoulding.
Some performance indicators of product：
After processing 15min again at 170 degrees Celsius of 10MPa, strain is restored to the 12.4% of primary sample.
Lack ester group in the high molecular material that comparative example 1 obtains, lack urea groups in the high molecular material that comparative example 2 obtains,
Lack ester group and urea groups in comparative example 3.The mechanical performance recovery of above three comparative example is markedly less than the shape that embodiment 1 obtains
Shape remembers high molecular material.
The specific implementation mode of the application above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
Cannot the limitation to the application protection domain therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, under the premise of not departing from technical scheme design, various modifications and improvements can be made, these belong to this
The protection domain of application.
Claims (8)
1. a kind of can process with triple dynamic keys and the shape-memory material of solid plastics again, it is characterised in that：The shape
Shape remembers the shape-memory material that high molecular material is covalent cross-linking, in the cross-linked network of shape memory high molecule comprising ester group,
Three kinds of dynamic keys of urea groups and carbamate groups.
2. a kind of can process with triple dynamic keys described in accordance with the claim 1 and the shape memory material of solid plastics again
Material, it is characterised in that：The shape memory high molecule is the material of polyester, polyureas and urethane crosslinks.
3. a kind of can process with triple dynamic keys described in accordance with the claim 1 and the shape memory material of solid plastics again
Material, which is characterized in that be made of the raw material of following parts by weight：
50-90 parts of polycaprolactone；
0.1-50 parts of monomer with the amido that is obstructed；
0.1-30 parts of trifunctional group cross-linking agent；
0.1-5 parts of catalyst；
10-300 parts of solvent.
4. a kind of can process with triple dynamic keys described in accordance with the claim 3 and the shape memory material of solid plastics again
Material, it is characterised in that：The polycaprolactone is the oligomer of weight average molecular weight 1000-3000.
5. a kind of can process with triple dynamic keys described in accordance with the claim 3 and the shape memory material of solid plastics again
Material, it is characterised in that：It is described to have the monomer for the amido that is obstructed for tertiary butyl ethanol amine or N, one in N'- di-t-butyl ethylenediamines
Kind or two kinds of combination.
6. a kind of can process with triple dynamic keys described in accordance with the claim 3 and the shape memory material of solid plastics again
Material, it is characterised in that：The trifunctional group cross-linking agent is (- three base of 2,4,6- trioxy-s triazine -1,3,5 (2H, 4H, 6H)) three
(hexa-methylene) isocyanates.
7. a kind of can process with triple dynamic keys described in accordance with the claim 3 and the shape memory material of solid plastics again
Material, it is characterised in that：The catalyst is the combination of one or both of dibutyl tin laurate or stannous iso caprylate.
8. a kind of can process with triple dynamic keys described in accordance with the claim 1 and the shape-memory material of solid plastics again
Preparation method, which is characterized in that include the following steps：Three kinds of ester group, urea groups and carbamate groups dynamics will be used to form
The polymerized monomer raw material and catalyst by proportion of key are added in solvent, and stirring and dissolving obtains solution at room temperature；Then solution is noted
Enter to react in mold, heating reaction, room temperature drying to obtain shape memory high molecule material after demoulding.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111590914A (en) * | 2020-05-29 | 2020-08-28 | 临沂大学 | 4D deformed reticulated hollowed degradable intravascular stent with concave-convex structures on inner and outer surfaces and preparation and use methods thereof |
| CN115010899A (en) * | 2021-07-30 | 2022-09-06 | 浙江大学 | Preparation method of polyurea acrylate oligomer, polyurea acrylate oligomer and application method of polyurea acrylate oligomer |
-
2018
- 2018-04-02 CN CN201810284143.8A patent/CN108586693A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111590914A (en) * | 2020-05-29 | 2020-08-28 | 临沂大学 | 4D deformed reticulated hollowed degradable intravascular stent with concave-convex structures on inner and outer surfaces and preparation and use methods thereof |
| CN115010899A (en) * | 2021-07-30 | 2022-09-06 | 浙江大学 | Preparation method of polyurea acrylate oligomer, polyurea acrylate oligomer and application method of polyurea acrylate oligomer |
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Application publication date: 20180928 |