CN113214475B - Preparation method of regenerated low-melting-point polyamide 6 elastomer - Google Patents
Preparation method of regenerated low-melting-point polyamide 6 elastomer Download PDFInfo
- Publication number
- CN113214475B CN113214475B CN202110483977.3A CN202110483977A CN113214475B CN 113214475 B CN113214475 B CN 113214475B CN 202110483977 A CN202110483977 A CN 202110483977A CN 113214475 B CN113214475 B CN 113214475B
- Authority
- CN
- China
- Prior art keywords
- polyamide
- elastomer
- melting
- point
- alcoholysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 186
- 229920001971 elastomer Polymers 0.000 title claims abstract description 88
- 239000000806 elastomer Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000002699 waste material Substances 0.000 claims abstract description 58
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 48
- 238000002844 melting Methods 0.000 claims abstract description 33
- 230000008018 melting Effects 0.000 claims abstract description 32
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 229920000570 polyether Polymers 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007112 amidation reaction Methods 0.000 claims abstract description 17
- 230000032050 esterification Effects 0.000 claims abstract description 17
- 238000005886 esterification reaction Methods 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 15
- 125000004185 ester group Chemical group 0.000 claims abstract 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 36
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 13
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 10
- 235000017281 sodium acetate Nutrition 0.000 claims description 10
- 239000001632 sodium acetate Substances 0.000 claims description 10
- 239000004246 zinc acetate Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 6
- 239000012760 heat stabilizer Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 16
- 229920003023 plastic Polymers 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 abstract description 2
- 150000002148 esters Chemical group 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- -1 polysiloxane Polymers 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 229920002725 thermoplastic elastomer Polymers 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- KRXBVZUTZPDWQI-UHFFFAOYSA-N ethane-1,2-diol;titanium Chemical compound [Ti].OCCO KRXBVZUTZPDWQI-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention relates to a preparation method of a regenerated low-melting-point polyamide 6 elastomer, which comprises the steps of firstly adding dihydric alcohol to carry out alcoholysis on waste polyamide 6 under a certain condition to generate alcoholysis polyamide 6 chain segments with hydroxyl and amino at two ends respectively, then adding dibasic acid and polyether chain segments to enable the alcoholysis polyamide 6 chain segments and the polyether chain segments to carry out esterification and amidation reactions with the dibasic acid respectively to realize chain growth, providing a reaction connecting group by the dibasic acid to carry out copolymerization on the alcoholysis polyamide 6 chain segments and the polyether chain segments, assisting in regulating and controlling the melting point of a polymer, and then balancing the molecular weight through an ester exchange reaction to prepare the regenerated low-melting-point polyamide 6 elastomer. By the method, the waste polyamide 6 can be recycled to be made into the polyamide 6 elastomer material, the number average molecular weight of the polyamide 6 chain segment after alcoholysis can be controlled by adjusting the amount of the added dihydric alcohol, and the domain distribution among the soft and hard segments can be adjusted. The regenerated polyamide 6 elastomer material can be widely applied to the fields of plastics, films and fibers.
Description
Technical Field
The invention belongs to the technical field of preparation of high-molecular copolymers, and relates to a preparation method of a regenerated low-melting-point polyamide 6 elastomer.
Background
Polyamide thermoplastic elastomers (TPAE), which are novel thermoplastic elastomers recently developed as compared with thermoplastic elastomers such as SBC (styrenes), TPO (polyolefins), TPVC (PVC), TPU (PU), and TPEE (polyesters), have entered a stable development phase after undergoing a development phase, a technical maturity phase, and a high-speed development phase as an important variety of polymer materials. TPAE has the advantages of high tensile strength and low-temperature impact strength, good flexibility, high elastic recovery rate, strong fatigue resistance, small friction coefficient, good sound absorption effect, good thermal stability, and long-term use at the maximum use temperature of 175 ℃ and 150 ℃, and the like. However, in the low temperature application field, the polyamide chain segment is crystallized along with the reduction of the temperature, the molecular chain loses the mobility, the elastomer gradually loses elasticity and is easy to become a brittle material, and the application of the polyamide in the field is limited. Therefore, lowering the melting point of the polymer and lowering the crystallization temperature accordingly have resulted in a wider temperature range for its application, and have been the focus of research in the present stage. In order to reduce the melting point of polyamide 6 elastomer, the prior art mainly copolymerizes the soft block and the hard block through end group chain polymerization, but the size of the hard block molecular weight is still uncontrollable and low due to the limitation of the end group content and the reaction point, and if the hard block molecular weight is directly polymerized by using monomers, the material loses the strength, thereby losing the application value.
In addition, TPAE has excellent physical and chemical properties, can be formed and processed by adopting injection, extrusion, blow molding and rotational molding processes, and can be adapted to various functional purposes through filling, strengthening and alloying composite modification. TPAE can be directly made into silicon rubber, fluororubber, nitrile rubber, TPEE, TPU and the like and substitutes of a plurality of thermoplastic plastics, has the characteristics of light weight, short processing period, low cost and the like, and enables the consumption to be increased year by year, and the existing polyamide elastomer material is mainly applied to blow molding or injection molding into plastic products. The new materials such as polyamide 6 elastomer meet the increasing new product requirements of people, but how to better find a balance point from the viewpoint of plastic pollution and new material development becomes the key point of continuous research and exploration of people at present. TPAE belongs to one of polyamide 6 copolymerization materials, and how to regenerate the waste polyamide 6 into a secondary material with special functions by a chemical method has important research and application values. Through the transformation mode, the pressure of plastics on environmental pollution is reduced while new materials are developed and the additional value of commodities is improved, and a rationalization direction is searched for the regeneration research and development of the polyamide 6 industry.
Therefore, it would be of great significance to develop a preparation method capable of recycling and developing polyamide 6 into a novel material.
Disclosure of Invention
The present invention has been made to solve the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide a method for producing a regenerated low-melting polyamide 6 elastomer. The alcoholysis and repolymerization mechanism of the polyamide 6 is simple and clear, and the requirement on required equipment is low. Firstly, carrying out alcoholysis on waste polyamide 6 and dihydric alcohol under a certain condition to generate an alcoholysis polyamide 6 chain segment with hydroxyl and amino at two ends, then adding dibasic acid and a polyether chain segment to enable the alcoholysis polyamide 6 chain segment and the polyether chain segment to respectively carry out esterification and amidation reactions with the dibasic acid to realize chain growth, wherein the dibasic acid provides a reaction connecting group to copolymerize the alcoholysis polyamide 6 chain segment and the polyether chain segment, and molecular weight is balanced through ester exchange reaction to prepare the regenerated low-melting-point polyamide 6 elastomer, wherein the alcoholysis polyamide 6 chain segment is used as a hard segment of the elastomer to provide a rigid structure, and the polyether chain segment is used as a soft segment of the elastomer to provide a flexible structure. And the number average molecular weight of the alcoholysis polyamide 6 chain segment can be controlled by adjusting the addition amount of the dihydric alcohol, and the domain distribution of soft and hard segments is adjusted, so that the melting point of the polymer is adjusted. The regenerated low-melting-point polyamide 6 elastomer material can be widely applied to the fields of plastics, films and fibers.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a regenerated low-melting-point polyamide 6 elastomer comprises the steps of adding dihydric alcohol into waste polyamide 6, carrying out alcoholysis under certain conditions to generate alcoholysis polyamide 6 chain segments with hydroxyl and amino at two ends respectively, and then adding a dibasic acid monomer to carry out esterification and amidation reactions with a polyether chain segment to realize chain growth to prepare the regenerated low-melting-point polyamide 6 elastomer.
As a preferred technical scheme:
the preparation method of the regenerated low-melting-point polyamide 6 elastomer comprises the following specific preparation steps:
(1) carrying out alcoholysis reaction on waste polyamide 6 and a certain amount of dihydric alcohol for 3-4 h at the temperature of 230-250 ℃ and under the pressure of 0.5-2 MPa to generate alcoholysis polyamide 6 chain segments with hydroxyl and amino at two ends respectively; the addition amount of the dihydric alcohol is 5-50 wt% of the waste polyamide 6;
(2) adding a certain amount of dibasic acid, polyether, a catalyst, a heat stabilizer and an ether inhibitor, and carrying out esterification and amidation reactions under the conditions that the temperature is 220-260 ℃ and the pressure is 0.01-0.5 MPa, wherein the reaction time is 3-4 h, the addition amount of the polyether is 80-120 wt% of that of the dibasic alcohol, and the addition amount of the dibasic acid is 180-220 wt% of the sum of the addition amounts of the dibasic alcohol and the polyether;
(3) carrying out transesterification reaction at the temperature of 260-290 ℃ and the pressure of 0.01-0.5 MPa to balance the molecular weight, and obtaining the regenerated low-melting-point polyamide 6 elastomer, wherein the reaction termination condition is that the molecular weight of the regenerated low-melting-point polyamide 6 elastomer is 14000-30000 g/mol.
The preparation method of the regenerated low-melting-point polyamide 6 elastomer comprises the step (1) that the dihydric alcohol is HO (CH) 2 ) n CH 2 OH、
Wherein n is 2-10, and m is 2-10.
According to the preparation method of the regenerated low-melting-point polyamide 6 elastomer, the number average molecular weight of the alcoholysis polyamide 6 chain segment in the step (1) is 500-6000 g/mol.
The preparation method of the regenerated low-melting-point polyamide 6 elastomer comprises the step (2) that the dibasic acid is HOOC (CH) 2 ) x More than one of COOH, terephthalic acid and phthalic acid, wherein x is 2-10.
In the preparation method of the regenerated low-melting-point polyamide 6 elastomer, in the step (2), the polyether is more than one of polyethylene glycol, polytetrahydrofuran and polysiloxane; the number average molecular weight of the polyether is 200-10000 g/mol.
According to the preparation method of the regenerated low-melting-point polyamide 6 elastomer, in the step (2), the catalyst is a titanium catalyst or an antimony catalyst, the heat stabilizer is triphenyl phosphite, and the ether inhibitor is sodium acetate or zinc acetate;
the addition amount of the catalyst, the heat stabilizer and the ether inhibitor is 10-500 ppm, 10-500 ppm and 300-500 ppm of the addition amount of the waste polyamide 6 in the step (1).
The preparation method of the regenerated low-melting-point polyamide 6 elastomer comprises the steps of preparing a titanium catalyst, wherein the titanium catalyst is tetrabutyl titanate and/or ethylene glycol titanium; the antimony catalyst is more than one of antimony trioxide, antimony acetate and ethylene glycol antimony.
The preparation method of the regenerated low-melting-point polyamide 6 elastomer has the advantages that the relative viscosity of the regenerated low-melting-point polyamide 6 elastomer is 2.4-3.6, the melting point is 130-190 ℃, and the number average molecular weight is 14000-30000 g/mol.
According to the preparation method of the regenerated low-melting-point polyamide 6 elastomer, the breaking strength of the regenerated low-melting-point polyamide 6 elastomer is 30-50 MPa, and the breaking elongation is 300-500%.
The invention mechanism is as follows:
in the prior art for preparing polyamide 6 elastomer, the polyamide 6 chain segment is mainly controlled by adding a certain amount of dibasic acid end capping agent in the process of hydrolytic polymerization of caprolactam, controlling the molecular weight of the polyamide 6 chain segment within a certain molecular weight range, and then carrying out copolymerization reaction with soft segments such as polyether and the like to prepare the polyamide 6 elastomer. In the prior art, caprolactam is used as a starting material and high polymers are used as final products, and only the development and application of new materials are considered. The invention prepares the new material of polyamide 6 by taking the waste polyamide 6 as the starting point of the new material preparation from the viewpoint of regeneration.
According to the invention, waste polyamide 6 is added with a small amount of diol to be alcoholyzed into a polyamide 6 chain segment with a certain molecular weight by an alcoholysis mode, dibasic acid and a polyether chain segment are added into the waste polyamide 6 chain segment in combination with the molecular structure characteristic of the polyamide 6 chain segment after alcoholysis to respectively carry out esterification and amidation reactions with two ends of the alcoholysis polyamide 6 chain segment to realize chain growth, and then the molecular weight is balanced through an ester exchange reaction to prepare the regenerated low-melting-point polyamide 6 elastomer. The dibasic acid serves as a linking group to provide a reaction point and assist in regulating the melting point of the copolymer. The diol is used as an alcoholysis agent, the number average molecular weight of a polyamide 6 chain segment after alcoholysis can be controlled by adjusting the added amount, the alcoholysis polyamide 6 chain segment is used as a hard segment chain segment in the regenerated polyamide 6 elastomer, the chain segment length and the crystallization capacity directly determine the melting point and the crystallization capacity of the regenerated low-melting-point polyamide 6 elastomer, and the chain segment phase domain and the melting point of a soft segment can be effectively controlled by controlling the chain segment length of the alcoholysis polyamide 6.
Has the advantages that:
(1) according to the preparation method of the regenerated low-melting-point polyamide 6 elastomer, disclosed by the invention, the polyamide 6 is alcoholyzed into a polyamide 6 chain segment with a certain molecular weight by adding the dihydric alcohol, the two ends of the polyamide 6 chain segment are respectively provided with the terminal amino and the terminal hydroxyl, and the molecular weight is increased by adding the dibasic acid and the polyether chain segment which are respectively used as a connecting group and a soft segment to carry out esterification and amidation reactions. Realizes the regeneration development of new materials from polyamide 6 high polymer to polyamide 6 base;
(2) according to the preparation method of the regenerated low-melting-point polyamide 6 elastomer, alcoholysis of the polyamide 6 chain segment can be realized by controlling the addition amount of the dihydric alcohol, the number average molecular weight of the polyamide 6 chain segment is controlled within a certain range, and the melting point and the phase domain of the polyamide 6 elastomer can be regulated and controlled by matching polyether chain segments with different molecular weights;
(3) according to the preparation method of the regenerated low-melting-point polyamide 6 elastomer, the dibasic acid is used as a linking monomer, the addition amount and the addition type can be designed according to the actual application requirements, and the auxiliary regulation and control of the melting point are realized;
(4) according to the preparation method of the regenerated low-melting-point polyamide 6 elastomer, the waste polyamide 6 plastic products and fiber products can be recycled and regenerated through a simple process, the regenerated low-melting-point polyamide 6 elastomer with certain functionality is prepared, and a recycling mode is provided for the waste polyamide 6.
Drawings
FIG. 1 shows the reaction process for regenerating a low melting polyamide 6 elastomer.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
FIG. 1 shows the reaction process of the regenerated low-melting-point polyamide 6 elastomer, wherein glycol reacts with waste amide 6 to form an alcoholysis polyamide 6 segment, and the alcoholysis polyamide 6 segment undergoes esterification and amidation with a diacid and a polyether segment to form the regenerated low-melting-point polyamide 6 elastomer.
Example 1
A method for preparing a regenerated low-melting-point polyamide 6 elastomer by using waste polyamide 6, wherein the waste polyamide 6 is in a curtain specific form and comprises the following specific preparation steps:
(1) waste polyamide 6 and HO (CH) 2 ) 2 CH 2 Carrying out alcoholysis reaction on OH at the temperature of 230 ℃ and the pressure of 2MPa for 3h to generate an alcoholysis polyamide 6 chain segment which is provided with hydroxyl and amino at two ends respectively and has the number average molecular weight of 500 g/mol;
HO(CH 2 ) 2 CH 2 the addition amount of OH is 50wt% of the waste polyamide 6;
(2) adding a certain amount of HOOC (CH) 2 ) 2 COOH, polyethylene glycol with the number average molecular weight of 200g/mol, tetrabutyl titanate, triphenyl phosphite and sodium acetate, and carrying out esterification and amidation reactions at the temperature of 220 ℃ and the pressure of 0.5MPa for 4 h;
the addition amount of polyethylene glycol is HO (CH) 2 ) 2 CH 2 80 wt% of the OH addition amount;
HOOC(CH 2 ) 2 the amount of COOH added was HO (CH) 2 ) 2 CH 2 The sum of the addition amounts of OH and polyethylene glycol is 180 wt%;
the addition amounts of tetrabutyl titanate, triphenyl phosphite and sodium acetate are 10ppm, 10ppm and 300ppm of the addition amount of the waste polyamide 6 in the step (1);
(3) the regenerated polyamide 6 elastomer with low melting point is prepared by ester exchange reaction under the conditions that the temperature is 260 ℃ and the pressure is 0.5MPa, and the molecular weight of the regenerated polyamide 6 elastomer with low melting point is 14000 g/mol.
The relative viscosity of the prepared regenerated low-melting-point polyamide 6 elastomer is 2.4, the melting point is 130 ℃, the breaking strength is 30MPa, and the breaking elongation is 500%.
Example 2
A method for preparing a regenerated low-melting-point polyamide 6 elastomer by using waste polyamide 6, wherein the waste polyamide 6 is a carpet in a specific form, and the method comprises the following specific preparation steps:
(1) waste polyamide 6 and
carrying out alcoholysis reaction for 3h at the temperature of 234 ℃ and the pressure of 1.8MPa to generate alcoholysis polyamide 6 chain segments which respectively have hydroxyl and amino at two ends and have the number average molecular weight of 1500 g/mol;
(2) adding a certain amount of HOOC (CH) 2 ) 10 COOH, polytetrahydrofuran with the number average molecular weight of 800, ethylene glycol titanium, triphenyl phosphite and sodium acetate, and carrying out esterification and amidation reactions under the conditions that the temperature is 230 ℃ and the pressure is 0.4MPa, wherein the reaction time is 4 h;
polytetrahydrofuran is added in an amount of
The addition amount is 110 wt%;
HOOC(CH 2 ) 10 the amount of COOH added was
190 wt% of the total amount of polytetrahydrofuran added;
the addition amounts of the titanium glycol, the triphenyl phosphite and the sodium acetate are 400ppm, 450ppm and 320ppm of the addition amount of the waste polyamide 6 in the step (1);
(3) the regenerated polyamide 6 elastomer with low melting point is prepared by ester exchange reaction under the conditions of 270 ℃ and 0.4MPa, and the molecular weight of the regenerated polyamide 6 elastomer with low melting point is 20000 g/mol.
The relative viscosity of the prepared regenerated low-melting-point polyamide 6 elastomer is 2.8, the melting point is 140 ℃, the breaking strength is 32MPa, and the breaking elongation is 470%.
Example 3
A method for preparing a regenerated low-melting-point polyamide 6 elastomer by using waste polyamide 6, wherein the waste polyamide 6 is a fishing net thread in a specific form, and the specific preparation steps are as follows:
(1) waste polyamide 6 and
carrying out alcoholysis reaction for 4h at the temperature of 238 ℃ and the pressure of 1.6MPa to generate alcoholysis polyamide 6 chain segments which respectively have hydroxyl and amino at two ends and have the number average molecular weight of 2500 g/mol;
(2) adding a certain amount of terephthalic acid, polysiloxane with the number average molecular weight of 2000g/mol, antimony trioxide, triphenyl phosphite and sodium acetate, and performing esterification and amidation reactions at the temperature of 240 ℃ and the pressure of 0.3MPa for 4 hours;
the polysiloxane is added in an amount of
90 wt% of the addition amount;
terephthalic acid is added in an amount of
215% by weight of the sum of the amounts of polysiloxane added;
the addition amounts of antimony trioxide, triphenyl phosphite and sodium acetate are 50ppm, 50ppm and 350ppm of the addition amount of the waste polyamide 6 in the step (1);
(3) the regenerated polyamide 6 elastomer with low melting point is prepared by ester exchange reaction under the conditions that the temperature is 275 ℃ and the pressure is 0.3MPa, and the molecular weight of the regenerated polyamide 6 elastomer with low melting point is 22000 g/mol.
The relative viscosity of the prepared regenerated low-melting-point polyamide 6 elastomer is 3, the melting point is 160 ℃, the breaking strength is 39MPa, and the breaking elongation is 390%.
Example 4
A method for preparing a regenerated low-melting-point polyamide 6 elastomer by using waste polyamide 6, wherein the waste polyamide 6 is in a nylon woven bag, and the method comprises the following specific preparation steps:
(1) waste polyamide 6 and
carrying out alcoholysis reaction for 4h at 242 ℃ and 1.4MPa to generate alcoholysis polyamide 6 chain segments with hydroxyl and amino at two ends respectively and with the number average molecular weight of 3600 g/mol;
(2) adding a certain amount of terephthalic acid, polyethylene glycol with the number average molecular weight of 4000g/mol, antimony acetate, triphenyl phosphite and sodium acetate, and performing esterification and amidation reactions at the temperature of 245 ℃ and the pressure of 0.2MPa for 3 hours;
the addition amount of polyethylene glycol is
100 wt% of the addition amount;
terephthalic acid is added in an amount of
210 wt% of the sum of the addition amount of polyethylene glycol;
the addition amounts of antimony acetate, triphenyl phosphite and sodium acetate are 300ppm, 100ppm and 400ppm of the addition amount of the waste polyamide 6 in the step (1);
(3) the regenerated polyamide 6 elastomer with low melting point is prepared by ester exchange reaction under the conditions that the temperature is 280 ℃ and the pressure is 0.2MPa, and the reaction termination condition is that the molecular weight of the regenerated polyamide 6 elastomer with low melting point is 17000 g/mol.
The relative viscosity of the prepared regenerated low-melting-point polyamide 6 elastomer is 2.6, the melting point is 150 ℃, the breaking strength is 35MPa, and the breaking elongation is 430%.
Example 5
A method for preparing a regenerated low-melting-point polyamide 6 elastomer by using waste polyamide 6, wherein the waste polyamide 6 is specifically an automobile interior, and the preparation method comprises the following specific steps:
(1) waste polyamide 6 and HO (CH) 2 ) 10 CH 2 Carrying out alcoholysis reaction on OH at the temperature of 246 ℃ and the pressure of 1MPa for 4h to generate an alcoholysis polyamide 6 chain segment which is provided with hydroxyl and amino at two ends respectively and has the number average molecular weight of 4800 g/mol;
HO(CH2) 10 CH 2 the addition amount of OH is 20wt% of the waste polyamide 6;
(2) adding a certain amount of phthalic acid, polytetrahydrofuran with the number average molecular weight of 6000g/mol, ethylene glycol antimony, triphenyl phosphite and zinc acetate, and performing esterification and amidation reactions at the temperature of 255 ℃ and the pressure of 0.1MPa for 3 h;
the amount of polytetrahydrofuran added is HO (CH) 2 ) 10 CH 2 95 wt% of OH addition;
the additive amount of phthalic acid is HO (CH) 2 ) 10 CH 2 205 wt% of the sum of the addition amounts of OH and polytetrahydrofuran;
the addition amounts of the ethylene glycol antimony, the triphenyl phosphite and the zinc acetate are 100ppm, 250ppm and 450ppm of the addition amount of the waste polyamide 6 in the step (1);
(3) the regenerated polyamide 6 elastomer with low melting point is prepared by ester exchange reaction under the conditions of 285 ℃ and 0.1MPa, and the molecular weight of the regenerated polyamide 6 elastomer with low melting point is 24000g/mol under the condition of reaction termination.
The relative viscosity of the prepared regenerated low-melting-point polyamide 6 elastomer is 3.2, the melting point is 170 ℃, the breaking strength is 43MPa, and the breaking elongation is 360%.
Example 6
A method for preparing a regenerated low-melting-point polyamide 6 elastomer by using waste polyamide 6, wherein the waste polyamide 6 is specifically in the form of a shell of a household appliance, and the preparation method specifically comprises the following steps:
(1) waste polyamide 6 and
carrying out alcoholysis reaction for 4h at 248 ℃ and 0.8MPa to obtain alcoholysis polyamide 6 chain segment with hydroxyl and amino at two ends and with number average molecular weight of 5200 g/mol;
(2) adding a certain amount of phthalic acid, polysiloxane with the number average molecular weight of 10000g/mol, a mixture of tetrabutyl titanate and ethylene glycol titanium with the mass ratio of 1:1, triphenyl phosphite and zinc acetate, and performing esterification and amidation reactions at the temperature of 258 ℃ and the pressure of 0.05MPa for 3 h;
the polysiloxane is added in an amount of
115 wt% of the addition amount;
phthalic acid is added in an amount of
200 wt% of the total amount of polysiloxane added;
the addition amounts of the mixture of tetrabutyl titanate and titanium glycol, triphenyl phosphite and zinc acetate are 200ppm, 350ppm and 470ppm of the addition amount of the waste polyamide 6 in the step (1);
(3) the regenerated low-melting-point polyamide 6 elastomer is prepared by ester exchange reaction under the conditions of 288 ℃ and 0.05MPa, and the molecular weight of the regenerated low-melting-point polyamide 6 elastomer is 28000 g/mol.
The relative viscosity of the prepared regenerated low-melting-point polyamide 6 elastomer is 3.4, the melting point is 180 ℃, the breaking strength is 47MPa, and the breaking elongation is 330%.
Example 7
A method for preparing a regenerated low-melting-point polyamide 6 elastomer by using waste polyamide 6, wherein the waste polyamide 6 is in a curtain specific form and comprises the following specific preparation steps:
(1) waste polyamide 6 and
carrying out alcoholysis reaction for 4h at the temperature of 250 ℃ and the pressure of 0.5MPa to generate alcoholysis polyamide 6 chain segments which respectively have hydroxyl and amino at two ends and have the number average molecular weight of 6000 g/mol;
(2) adding a certain amount of a mixture of terephthalic acid and phthalic acid with the mass ratio of 1:1, a mixture of polyethylene glycol (with the number average molecular weight of 200g/mol) and polysiloxane (with the number average molecular weight of 2000g/mol) with the mass ratio of 1:1, a mixture of antimony trioxide and antimony acetate with the mass ratio of 1:1, triphenyl phosphite and zinc acetate, and performing esterification and amidation reactions at the temperature of 260 ℃ and the pressure of 0.01MPa for 3 h;
the addition amount of the mixture of polyethylene glycol and polytetrahydrofuran is
120wt% of the addition amount;
the mixture of terephthalic acid and phthalic acid is added in an amount of
220wt% of the total amount of the mixture of polyethylene glycol and polytetrahydrofuran;
the addition amounts of the mixture of antimony trioxide and antimony acetate, triphenyl phosphite and zinc acetate are 500ppm, 500ppm and 500ppm of the addition amount of the waste polyamide 6 in the step (1);
(3) the regenerated polyamide 6 elastomer with low melting point is prepared by ester exchange reaction under the conditions that the temperature is 290 ℃ and the pressure is 0.01MPa, and the molecular weight of the regenerated polyamide 6 elastomer with low melting point is 30000g/mol under the condition of reaction termination.
The relative viscosity of the prepared regenerated low-melting-point polyamide 6 elastomer is 3.6, the melting point is 190 ℃, the breaking strength is 50MPa, and the breaking elongation is 300%.
Example 8
A method for preparing a regenerated low-melting-point polyamide 6 elastomer by using waste polyamide 6, wherein the waste polyamide 6 is a carpet in a specific form, and the method comprises the following specific preparation steps:
(1) waste polyamide 6 and
carrying out alcoholysis reaction for 3h at 236 ℃ and 1.7MPa to generate alcoholysis polyamide 6 chain segments with hydroxyl and amino at two ends respectively and with the number average molecular weight of 1800 g/mol;
(2) adding a certain amount of HOOC (CH) 2 ) 5 COOH, polytetrahydrofuran with the number average molecular weight of 900g/mol, ethylene glycol titanium, triphenyl phosphite and zinc acetate, and carrying out esterification and amidation reactions at the temperature of 235 ℃ and the pressure of 0.35MPa for 4 h;
polytetrahydrofuran is added in an amount of
The addition amount is 100wt％；
HOOC(CH 2 ) 5 The amount of COOH added was
206 wt% of the sum of the amounts of polytetrahydrofuran added;
the addition amounts of the titanium glycol, the triphenyl phosphite and the zinc acetate are 46ppm, 400ppm and 330ppm of the addition amount of the waste polyamide 6 in the step (1);
(3) the regenerated low-melting-point polyamide 6 elastomer is prepared by ester exchange reaction under the conditions that the temperature is 272 ℃ and the pressure is 0.4MPa, and the molecular weight of the regenerated low-melting-point polyamide 6 elastomer is 21000g/mol under the condition of reaction termination.
The relative viscosity of the prepared regenerated low-melting-point polyamide 6 elastomer is 2.9, the melting point is 150 ℃, the breaking strength is 37MPa, and the breaking elongation is 430%.
Claims (5)
1. A preparation method of a regenerated low-melting-point polyamide 6 elastomer is characterized by comprising the following steps: firstly, adding dihydric alcohol into waste polyamide 6, carrying out alcoholysis under certain conditions to generate alcoholysis polyamide 6 chain segments with hydroxyl and amino at two ends respectively, and then adding a dibasic acid monomer to carry out esterification and amidation reactions with a polyether chain segment to prepare a regenerated low-melting-point polyamide 6 elastomer;
the relative viscosity of the regenerated low-melting-point polyamide 6 elastomer is 2.4-3.6, and the melting point is 130-190 ℃;
the specific preparation steps of the regenerated low-melting-point polyamide 6 elastomer are as follows:
(1) carrying out alcoholysis reaction on waste polyamide 6 and a certain amount of dihydric alcohol for 3-4 h at the temperature of 230-250 ℃ and under the pressure of 0.5-2 MPa to generate alcoholysis polyamide 6 chain segments with hydroxyl and amino at two ends respectively; the addition amount of the dihydric alcohol is 5-50 wt% of the waste polyamide 6;
(2) adding a certain amount of dibasic acid, polyether, a catalyst, a heat stabilizer and an ether inhibitor, and performing esterification and amidation reaction at the temperature of 220-260 ℃ and the pressure of 0.01-0.5 MPa for 3-4 h, wherein the addition amount of the polyether is 80-120 wt% of that of the dibasic alcohol, and the addition amount of the dibasic acid is 180-220 wt% of the sum of the addition amounts of the dibasic alcohol and the polyether;
(3) performing ester exchange reaction at the temperature of 260-290 ℃ and the pressure of 0.01-0.5 MPa to prepare the regenerated low-melting-point polyamide 6 elastomer, wherein the reaction termination condition is that the molecular weight of the regenerated low-melting-point polyamide 6 elastomer is 14000-30000 g/mol;
the dihydric alcohol in the step (1) is HO (CH) 2 ) n CH 2 OH、
And
wherein n is 2-10, m is 2-10;
the dibasic acid in the step (2) is HOOC (CH) 2 ) x More than one of COOH, terephthalic acid and phthalic acid, wherein x is 2-10;
in the step (2), the polyether is more than one of polyethylene glycol and polytetrahydrofuran; the number average molecular weight of the polyether is 200-10000 g/mol.
2. The method for preparing a recycled low-melting-point polyamide 6 elastomer as claimed in claim 1, wherein the number-average molecular weight of the alcoholysis polyamide 6 segment in step (1) is 500-6000 g/mol.
3. The method for preparing regenerated low-melting-point polyamide 6 elastomer as claimed in claim 1, wherein the catalyst in step (2) is titanium catalyst or antimony catalyst, the heat stabilizer is triphenyl phosphite, and the anti-ether agent is sodium acetate or zinc acetate;
the addition amount of the catalyst, the heat stabilizer and the ether inhibitor is 10-500 ppm, 10-500 ppm and 300-500 ppm of the addition amount of the waste polyamide 6 in the step (1).
4. The method for preparing regenerated low-melting-point polyamide 6 elastomer according to claim 3, characterized in that the titanium catalyst is tetrabutyl titanate and/or titanium glycol; the antimony catalyst is more than one of antimony trioxide, antimony acetate and ethylene glycol antimony.
5. The method for preparing the regenerated low-melting-point polyamide 6 elastomer as claimed in claim 4, wherein the regenerated low-melting-point polyamide 6 elastomer has a breaking strength of 30-50 MPa and an elongation at break of 300% -500%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110483977.3A CN113214475B (en) | 2021-04-30 | 2021-04-30 | Preparation method of regenerated low-melting-point polyamide 6 elastomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110483977.3A CN113214475B (en) | 2021-04-30 | 2021-04-30 | Preparation method of regenerated low-melting-point polyamide 6 elastomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113214475A CN113214475A (en) | 2021-08-06 |
| CN113214475B true CN113214475B (en) | 2022-08-23 |
Family
ID=77090731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110483977.3A Active CN113214475B (en) | 2021-04-30 | 2021-04-30 | Preparation method of regenerated low-melting-point polyamide 6 elastomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113214475B (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62135521A (en) * | 1985-12-10 | 1987-06-18 | Daicel Chem Ind Ltd | Carboxyl group-terminated polycaprolactone |
| NL1006575C2 (en) * | 1997-07-14 | 1999-01-15 | Dsm Nv | Depolymerization of polyamides. |
| KR101160352B1 (en) * | 2004-03-26 | 2012-06-26 | 김도균 | Highly functional resin recycled polyester and polyamide hybrid waste and its manufacturing method |
| US8889821B2 (en) * | 2010-05-19 | 2014-11-18 | Mitsubishi Gas Chemical Company, Inc. | Polyester amide compound |
| CN108794742A (en) * | 2018-05-16 | 2018-11-13 | 广东圆融新材料有限公司 | Polyester-type polyamide 6 thermoplastic elastomer (TPE) and its synthetic method |
| CN109749079B (en) * | 2018-11-26 | 2020-04-17 | 东华大学 | Bio-based degradable polyamide 6 copolymer and preparation method thereof |
| CN110760097A (en) * | 2019-11-15 | 2020-02-07 | 余姚大发化纤有限公司 | Method for separating polyester and polyamide depolymerization from polyamide-containing waste polyester material |
-
2021
- 2021-04-30 CN CN202110483977.3A patent/CN113214475B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113214475A (en) | 2021-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105566639B (en) | A kind of 1012 based thermoplastic elastomeric material of polyamide and preparation method thereof | |
| CN109988300A (en) | A kind of super-low-hardness Long Carbon Chain Polyamide elastomer and preparation method thereof | |
| US9688813B2 (en) | Thermoplastic polyester elastomer and method for manufacturing the same | |
| CN106188513B (en) | A kind of synthetic method of polyetherester block copolymer | |
| WO2001014447A1 (en) | Polyetherester elastomer | |
| CN111004389B (en) | Preparation method of polyamide elastomer | |
| US7705109B2 (en) | Block copolyetherester elastomer and preparation thereof | |
| CN105348522A (en) | Polyether block polyamide copolymer and synthesis method thereof | |
| EP2294141B1 (en) | End capping additive for polycondensate polymer resins | |
| CN113214475B (en) | Preparation method of regenerated low-melting-point polyamide 6 elastomer | |
| CN113248705B (en) | Alcoholysis regeneration method and application of waste polyester-polyamide 6 blended textile | |
| CN107698771B (en) | High-resilience PA6 series thermoplastic elastomer and preparation method thereof | |
| CN109320726B (en) | High-resilience thermoplastic elastomer and preparation method thereof | |
| WO2012102792A1 (en) | Polymeric compositions comprising polylactic acid oligomers and methods of making the same | |
| CN110066388A (en) | A kind of thermoplastic polyester elastomer foaming precursor and foaming body | |
| KR101551633B1 (en) | Polyether Ester Elastomer and Manufacturing Method therof | |
| CN106478930B (en) | Preparation method of thermoplastic polyester elastomer base material | |
| CN109320699B (en) | Thermoplastic aliphatic-aromatic copolyester elastomer and preparation method thereof | |
| CN115521448B (en) | Copolymerization modified polypropylene carbonate copolymer, and preparation method and application thereof | |
| Djonlagic et al. | Thermoplastic copolyester elastomers | |
| KR101433898B1 (en) | Polyether Ester Elastomer with Excellent Thermal Stability and Method of Preparing Same | |
| CN103724599B (en) | A kind of synthetic method of poly butylene succinate | |
| CN108586734B (en) | Polyester-type polyamide 6 elastomer and its synthetic method | |
| KR102328190B1 (en) | Polyetherester elastomer resin with transparency and Molding procuced from the same | |
| US3190862A (en) | Copolymers of ethylene and methyl substituted alpha, omega-diolefins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231122 Address after: 265706 Nanshan Industrial Park, Dongjiang Town, Longkou City, Yantai City, Shandong Province Patentee after: SHANDONG NANSHAN ZHISHANG TECHNOLOGY Co.,Ltd. Address before: 201620 No. 2999 North Renmin Road, Shanghai, Songjiang District Patentee before: DONGHUA University |
|
| TR01 | Transfer of patent right |