CN104497284B - Modified poly ester and its preparation method - Google Patents
Modified poly ester and its preparation method Download PDFInfo
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- CN104497284B CN104497284B CN201510023920.XA CN201510023920A CN104497284B CN 104497284 B CN104497284 B CN 104497284B CN 201510023920 A CN201510023920 A CN 201510023920A CN 104497284 B CN104497284 B CN 104497284B
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Abstract
The present invention relates to modified poly ester and its preparation method, the technical problem of poor processability is moulded in the suction mainly solving modified poly ester in prior art, utilize a kind of modified poly ester by adopting, adopt and comprise the reaction raw materials copolymerization of linking agent, properties-correcting agent, terephthalic acid and ethylene glycol and obtain; The molecule of described linking agent has the functional group that can form at most 3 or more than 3 crosslinked links in described modified poly ester; Described properties-correcting agent is selected from diacid properties-correcting agent and/or glycol modification agent, described diacid modifier molecules has 2 hydroxy-acid groups, the technical scheme in described glycol modification agent molecule with 2 alcohol hydroxyls, solves this technical problem preferably, can be used in the industrial production of modified poly ester.
Description
Technical field
The present invention relates to modified poly ester and its preparation method.
Background technology
Poly-diacid diol ester, especially polyethylene terephthalate (are called for short PET), are conventional thermoplastic polyesters. But different field, varies to the requirement of polyester property, in order to meet the needs of different field different performance, arisen at the historic moment in prior art various different modified poly ester and method of modifying different accordingly.
CN1566180A discloses a kind of method preparing modified poly ester, and it adopts terephthalic acid, m-phthalic acid and ethylene glycol to be that comonomer obtains by copolymerization taking m-phthalic acid as the modified poly ester of properties-correcting agent.
CN102964574A discloses a kind of method of modified poly ester and modification thereof, and it adopts m-phthalic acid, neopentyl glycol, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol copolymerization to obtain modified poly ester. Owing to m-phthalic acid, neopentyl glycol and 1,4 cyclohexane dimethanol are as properties-correcting agent, it is not only possible to improve the shrinking percentage of modified poly ester, and its fragility can be reduced so that it is as during bottle label, the phenomenons such as fracture can not occur, it is to increase yield rate.
CN102964575A discloses a kind of modified poly ester and its preparation method, and it adopts m-phthalic acid, neopentyl glycol, terephthalic acid and ethylene glycol copolymerization to obtain modified poly ester. M-phthalic acid and neopentyl glycol can not only improve the shrinking percentage of modified poly ester as properties-correcting agent, and can reduce its fragility so that it is as during bottle label, the phenomenons such as fracture can not occur, it is to increase yield rate.
CN102964576A discloses a kind of modified poly ester and its preparation method, and it adopts m-phthalic acid, terephthalic acid, 1,4 cyclohexane dimethanol and ethylene glycol copolymerization to obtain modified poly ester, and it has higher film and draws high intensity and elongation at break.
CN103665352A discloses the preparation method that environment-friendly type covers the dedicated modified polyester slice of iron, and it adopts ethylene glycol, 1,4 cyclohexane dimethanol, neopentyl glycol, terephthalic acid, m-phthalic acid copolymerization to obtain modified poly ester
CN103755941A discloses the method for modifying of a kind of polyester, and polyester and chainextender are carried out being obtained by reacting required modified poly ester by it.
But poor processability is moulded in the suction of modified poly ester of the prior art.
Summary of the invention
One of technical problem to be solved by this invention is the technical problem that poor processability is moulded in the suction of existing modified poly ester, it is provided that a kind of new modified poly ester, and it is for the base-material of case board, has the advantages that to inhale and mould good processability.
The two of technical problem to be solved by this invention are to provide the preparation method of the described modified poly ester of one of above-mentioned technical problem.
The three of technical problem to be solved by this invention are the application of the described modified poly ester of one of technical problem in case board.
For one of solving the problems of the technologies described above, the technical scheme of the present invention is as follows: a kind of modified poly ester, limiting viscosity is 0.7��1.4dl/g, and fusing point is 170-240 DEG C, adopts and comprises the reaction raw materials copolymerization of linking agent, properties-correcting agent, terephthalic acid and ethylene glycol and obtain; The molecule of described linking agent has the functional group that can form at most 3 or more than 3 crosslinked links in described modified poly ester; Described properties-correcting agent is selected from diacid properties-correcting agent and/or glycol modification agent, has 2 hydroxy-acid groups in described diacid modifier molecules, has 2 alcohol hydroxyls in described glycol modification agent molecule; Taking molar ratio computing (terephthalic acid+diacid properties-correcting agent): (ethylene glycol+glycol modification agent): linking agent is as 1:(1.1��2.0): (0.001��0.005), the mol ratio of diacid properties-correcting agent and terephthalic acid is a, and the mol ratio of glycol modification agent and ethylene glycol is b; A+b=0.10��0.45.
In technique scheme, described limiting viscosity preferably 0.7��1.2dl/g, it is more preferable to 0.74��1.0dl/g.
In technique scheme, described fusing point preferably 180��230 DEG C, it is most preferred that 190��230 DEG C.
In technique scheme, in a and b, one of them can be 0 can also not be all 0. Such as during b=0, technique scheme turns into: (terephthalic acid+diacid properties-correcting agent): ethylene glycol: linking agent is 1:(1.1��2.0): (0.001��0.005), the mol ratio of diacid properties-correcting agent and terephthalic acid is a, a=0.10��0.45. Again during such as a=0, technique scheme turns into: terephthalic acid: (ethylene glycol+glycol modification agent): linking agent is 1:(1.1��2.0): (0.001��0.005), the mol ratio of diacid properties-correcting agent and terephthalic acid is b, b=0.10��0.45. But when a and b is not all 0, relatively in a and b, one of them is that 0 technical scheme has better technique effect.
In technique scheme, with molar ratio computing (terephthalic acid+diacid properties-correcting agent): (ethylene glycol+glycol modification agent): linking agent is preferably 1:(1.1��1.5): (0.001��0.005).
In technique scheme, described linking agent is at least one in the acid anhydrides of polyvalent alcohol, polyprotonic acid or polyprotonic acid preferably, and described many units are 3 yuan or more than 3 yuan. First number of many units herein, it is possible to be integer such as but not limited to 3 yuan, 4 members, 5 yuan, 6 yuan, 7 yuan etc.; Unit's number can also be decimal. Can be obtained by mixing in required ratio with the linking agent of different unit. The number of the crosslinked link that the acid anhydrides of described polyvalent alcohol, polyprotonic acid or polyprotonic acid can be formed at most in described modified poly ester is identical with described first number.
In technique scheme, described linking agent more preferably comprises polyvalent alcohol and polyprotonic acid simultaneously, or more preferably comprises the acid anhydrides of polyvalent alcohol and polyprotonic acid simultaneously. Now, mould in the suction improving modified poly ester and there is in processing characteristics obvious synergy, particularly reducing be full of cracks, hang, in stream or the probability that turns white, there is obvious synergy.
In technique scheme, described polyvalent alcohol is at least one in tetramethylolmethane, dipentaerythritol, tripentaerythritol, TriMethylolPropane(TMP), trimethylolethane and glycerine preferably.
In technique scheme, the acid anhydrides of described polyprotonic acid is preferably pyromellitic acid anhydride.
In technique scheme, described polyprotonic acid is at least one in trimesic acid and Pyromellitic Acid preferably.
In technique scheme, described diacid properties-correcting agent is preferably m-phthalic acid and/or hexanodioic acid, more preferably adopt m-phthalic acid and hexanodioic acid, m-phthalic acid and hexanodioic acid reducing be full of cracks, hang stream and having synergy in the probability occurred that turns white simultaneously.
In technique scheme, described glycol modification agent is preferably neopentyl glycol and/or 1,4-butyleneglycol, it is more preferable to adopts neopentyl glycol and 1,4-butyleneglycol, neopentyl glycol and 1,4-butyleneglycol to hang in reduction in the probability flowing and turning white simultaneously and has synergy.
Enumerating as enforcement the non-limiting of mode, described modified poly ester can be obtained by following enforcement mode:
Enforcement mode 1: obtain by the reaction raw materials copolymerization comprising terephthalic acid, m-phthalic acid, ethylene glycol and tetramethylolmethane;
Enforcement mode 2: obtain by the reaction raw materials copolymerization comprising terephthalic acid, m-phthalic acid, ethylene glycol and pyromellitic acid anhydride;
Enforcement mode 3: obtain by the reaction raw materials copolymerization comprising terephthalic acid, m-phthalic acid, ethylene glycol and Pyromellitic Acid;
Enforcement mode 4: obtain by the reaction raw materials copolymerization comprising terephthalic acid, m-phthalic acid, ethylene glycol, tetramethylolmethane and pyromellitic acid anhydride;
Enforcement mode 5: obtain by the reaction raw materials copolymerization comprising terephthalic acid, hexanodioic acid, ethylene glycol, tetramethylolmethane and pyromellitic acid anhydride;
Enforcement mode 6: obtain by the reaction raw materials copolymerization comprising terephthalic acid, m-phthalic acid, hexanodioic acid, ethylene glycol, tetramethylolmethane and pyromellitic acid anhydride;
Enforcement mode 7: obtain by the reaction raw materials copolymerization comprising terephthalic acid, m-phthalic acid, hexanodioic acid, neopentyl glycol, ethylene glycol, tetramethylolmethane and pyromellitic acid anhydride;
Enforcement mode 8: obtain by the reaction raw materials copolymerization comprising terephthalic acid, m-phthalic acid, hexanodioic acid, 1,4-butyleneglycol, ethylene glycol, tetramethylolmethane and pyromellitic acid anhydride;
Enforcement mode 9: obtain by the reaction raw materials copolymerization comprising terephthalic acid, m-phthalic acid, hexanodioic acid, neopentyl glycol, 1,4-butyleneglycol, ethylene glycol, tetramethylolmethane and pyromellitic acid anhydride.
The limiting viscosity of modified poly ester of the present invention is adopted and is measured with the following method:
5.1.1 method A (capillary viscosimetry) in GB/T14190-2008 " fiber polyester chip (PET) test method ".
The fusing point of modified poly ester of the present invention is adopted and is measured with the following method:
5.3.1 method A (microscopy) in GB/T14190-2008 " fiber polyester chip (PET) test method ".
For solve the problems of the technologies described above two, the technical scheme of the present invention is as follows: the preparation method of modified poly ester according to any one of the technical scheme of one of above-mentioned technical problem, comprises the steps:
(1) make described reaction raw materials carry out esterification and obtain carboxylate;
(2) precondensation;
(3) polycondensation.
In technique scheme, the temperature of described esterification is preferably 240��280 DEG C.
In technique scheme, described esterification preferably proceeds to esterification yield and is at least 95%, and such as 95��99%. The formula that wherein esterification yield is natural is defined as follows:
The weight of esterification yield %=[esterification actual generation water/(in reaction raw materials, hydroxyl and carboxyl are generated the weight of water by the thorough esterification of metering)] �� 100%.
In technique scheme, the temperature of described prepolymerization reaction is preferably 260��290 DEG C.
In technique scheme, the reaction times of described prepolymerization reaction is preferably 0.5��2 hour.
In technique scheme, during prepolymerization reaction, reaction pressure is preferably transitioned into 500��700Pa gradually from normal atmosphere. The transition of reaction pressure can realize by vacuumizing operation.
In technique scheme, the condition of described prepolymerization reaction is more optimizedly: the temperature of described prepolymerization reaction is 260��290 DEG C, the reaction times of described prepolymerization reaction is 0.5��2 hour, and during prepolymerization reaction, reaction pressure is transitioned into 500��700Pa gradually from normal atmosphere.
In technique scheme, the temperature of described polycondensation is preferably 270��290 DEG C.
In technique scheme, the pressure of described polycondensation preferably 60��100Pa.
In technique scheme, described polycondensation reaction time preferably 2��5 hours.
In technique scheme, the condition of described polycondensation more preferably: the temperature of described polycondensation is 270��290 DEG C, the pressure of described polycondensation preferably 60��100Pa, and described polycondensation reaction time is 2��5 hours.
In technique scheme, those skilled in the art will know that, esterif iotacation step can add catalyzer, it is also possible to without catalyzer. Precondensation and polycondensation need to add polymerizing catalyst usually. Polymerizing catalyst is not particularly limited, and conventional those in polyester field all may be used for the present invention. Described polymerizing catalyst is such as but is not limited to antimony system polymerizing catalyst, titanium system polymerizing catalyst. As non-limiting the enumerating of polymerizing catalyst of antimony system, it is possible to be at least one in antimony glycol, antimonous oxide or antimony acetate. When esterif iotacation step adds catalyzer, it is possible to added in esterif iotacation step by polymerizing catalyst, these polymerizing catalysts also can play the effect of catalyzer in esterif iotacation step. As for the consumption of catalyzer, it does not have limit especially, such as, taking the gross weight of esterification raw material as benchmark, the consumption of catalyzer can be but be not limited to 0.005%��0.1%, more usually 0.01��0.1%.
After esterif iotacation step (such as but not limited to after esterif iotacation step and precondensation before), it is possible to according to the other side performance of modified poly ester need add those common auxiliary agents of this area. These auxiliary agents are such as but at least one that is not limited in oxidation inhibitor, fire retardant, matting agent, pigment, ultra-violet stabilizer etc.
For solve the problems of the technologies described above three, the technical scheme of the present invention is as follows: the application of modified poly ester according to any one of the technical scheme of one of above-mentioned technical problem in case board.
First the basic application method of described modified poly ester in case board it may be that make case and bag sheet material, and the plastics sucking moulding that then sheet material carry out case and bag obtains the shell of case and bag.
Following method such as can be adopted to prepare described sheet material:
By weight percentage, the toughner of the modified poly ester described in 60��95wt% and 5��40wt% is blended, then it is shaped to sheet material.
In technique scheme, the at least one of described toughner preferably from linear low density polyethylene (LLDPE), ultra-low density polyethylene (VLLDPE), Hydrogenated thermoplastic's styrene-butadiene rubber(SBR) (SEBS), polypropylene (PP), ethylene-propylene copolymer, ethylene-acrylic acid copolymer (EAA), ethylene-vinyl acetate copolymer (EVA), in the styrene-butadiene rubber(SBR) (SBR g MAH) of ethylene-methacrylic acid copolymer (EMMA), ethylene-methyl methacrylate glycidyl ester (GMA) and maleic anhydride graft.
In technique scheme, blended and shaping optional screw extrusion press coordinates flat-die to extrude; Described screw extrusion press more preferably twin screw extruder.
In technique scheme, in the preparation process of sheet material, in order to provide decoration function to sheet material, it is also possible to comprising the step carrying out with surface decoration film fitting further, the sheet material obtained is then the composition board with decorating film.
Sheet material involved in the performance of table 2 sheet material in the specific embodiment of the invention all adopts following preparation method to obtain:
The Korea S SK of the modified poly ester and 20wt% of getting 80wt% produces, the trade mark is the LLDPE of FV149M, the pellet of described modified poly ester and LLDPE is simply mixed, then adopting twin screw extruder to carry out blended and flat-die and extrude that to obtain thickness be 2.8mm, width is the sheet material of 660mm.
Adopting the auspicious ZSE60MAXX type twin screw extruder that hereby mechanical (granary) company limited produces of Leicester in the specific embodiment of the invention, screw diameter OD is 61.9mm.
The operating parameters of the twin screw extruder that the sheet material related in the specific embodiment of the invention adopts in preparation is: screw rod working speed is 100rpm, service temperature (from spout to mould head): first paragraph 160 DEG C, the 2nd section 210 DEG C, the 3rd section 230 DEG C, the 4th section and the 5th section 250 DEG C, the 6th section 240 DEG C, the 7th and the 8th section 230 DEG C, the 9th and the tenth section 220 DEG C, the 11 and the 12 section be 210 DEG C.
In the specific embodiment of the invention, the performance test methods of sheet material is as follows:
Tensile stress (fracture, 23 DEG C), adopts ASTMD256 method;
Tension strain (fracture, 23 DEG C), adopts ASTMD256 method;
Modulus in flexure (23 DEG C), adopts ASTMD796 method;
Izod notched impact strength (local fracture, 23 DEG C), adopts ASTMD368 method.
Plastics sucking moulding
Plastics sucking moulding itself is technology well known in the art, those skilled in the art will know that processing parameter is moulded in the suction how determining to be suitable for described sheet material.
The HL-211 type plastic suction forming apparatus moulded processing characteristics employing Ningbo Heng Yan packaging facilities factory and manufacture inhaled by the sheet material of specific embodiment of the invention table 3, moulds step acquisition by following concrete suction:
1, corresponding for above-mentioned table 2 plate cutting become thickness be 2.8mm, width be 660mm, length to be the sheet unit of 860mm;
2, sheet unit is placed in fixed position, then presses down by stationary installation, pin;
3, described sheet unit being advanced heating chamber, carry out adding thermal softening, Heating temperature is 150 DEG C, and heat-up time is 60 seconds;
4, softening sheet unit is released, blow swollen with 25 DEG C of pressurized air, blow about 3 seconds swollen time, time delay 1 second;
5, sheet unit and mould laminating is then made by bleeding, and to maintain sheet unit and mould time of fitting be 10 seconds;
6, cool, on shaping sheet unit, blow by cold blast engine and cool, about 15 seconds air blowing time, then carry out water-spraying control so that sheet unit fast cooling;
7, the demoulding, obtains Case outer-shell.
It is that 100 respective plates unit carry out 100 parallel suctions and mould and test the result that obtains that processing characteristics data are moulded in suction in table 3.
Inhaling the various phenomenons do not wished to see moulded in test and occur to plastics sucking moulding impact difference. Endangering maximum is blow quick-fried, directly causes plastics sucking moulding failure; The be full of cracks, the extension that occur on plastics sucking moulding successfully basis flow or turn white, and cause the Case outer-shell quality defect that plastics sucking moulding obtains. Different according to the probability that corresponding phenomenon occurs, by as follows for result classification:
Best: the probability that corresponding phenomenon occurs is 0%��it is less than 5%;
Better: the probability that corresponding phenomenon occurs is 5%��it is less than 20%;
Poor: the probability that corresponding phenomenon occurs is 20%��it is less than 60%;
Worst: the probability that corresponding phenomenon occurs is 60%��100%.
Embodiment
[embodiment 1]
1, the preparation of modified poly ester
The reactor of 1000 liters adds esterification raw material and polymerizing catalyst. Wherein esterification raw material is terephthalic acid, m-phthalic acid, ethylene glycol and tetramethylolmethane, esterification raw material gross weight 400 kilograms, taking molar ratio computing (terephthalic acid+m-phthalic acid): ethylene glycol: tetramethylolmethane is as 1:1.2:0.003, the mol ratio of m-phthalic acid and terephthalic acid is 0.2, polymerizing catalyst is antimony acetate, and consumption is 200 grams. Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97% to esterification yield, obtain esterification material in esterification reaction process.
Then, being 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk reaction period, reaction pressure is evacuated down to 600Pa gradually from normal atmosphere.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the temperature of reaction polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester limiting viscosity and fusing point
For ease of comparing, limiting viscosity and fusing point are arranged in table 1.
3, plate property test
For ease of comparing, the performance of sheet material is arranged in table 2.
4, plastics sucking moulding test
Prepared sheet material is used for the test of case and bag plastics sucking moulding, test-results is arranged in table 3.
[comparative example 1]
1, the preparation of modified poly ester
Do not adopt linking agent as different from Example 1, it be specially:
The reactor of 1000 liters adds esterification raw material and polymerizing catalyst. Wherein esterification raw material is terephthalic acid, m-phthalic acid and ethylene glycol, esterification raw material gross weight 400 kilograms, taking molar ratio computing (terephthalic acid+m-phthalic acid): ethylene glycol is as 1:1.2, the mol ratio of m-phthalic acid and terephthalic acid is 0.2, polymerizing catalyst is antimony acetate, and consumption is 200 grams. Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97% to esterification yield, obtain esterification material in esterification reaction process.
Then, being 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk reaction period, reaction pressure is evacuated down to 600Pa gradually from normal atmosphere.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the temperature of reaction polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester limiting viscosity and fusing point
For ease of comparing, limiting viscosity and fusing point are arranged in table 1.
3, plate property test
For ease of comparing, the performance of sheet material is arranged in table 2.
4, plastics sucking moulding test
Prepared sheet material is used for the test of case and bag plastics sucking moulding, test-results is arranged in table 3.
By the data of embodiment in table 2 and table 31 with comparative example 1 are compared it will be seen that add linking agent in preparation process due to modified poly ester, it is to increase the tensile stress of sheet material, draw high strain, modulus in flexure and shock strength. The more important thing is that processing characteristics is moulded in the suction that improve sheet material, it is embodied in significantly reduce and blows the raw probability of outburst, and reduce be full of cracks and hang the probability flowing and occurring.
[embodiment 2]
1, the preparation of modified poly ester
The reactor of 1000 liters adds esterification raw material and polymerizing catalyst. Wherein esterification raw material is terephthalic acid, m-phthalic acid, ethylene glycol and pyromellitic acid anhydride, esterification raw material gross weight 400 kilograms, taking molar ratio computing (terephthalic acid+m-phthalic acid): ethylene glycol: pyromellitic acid anhydride is as 1:1.2:0.003, the mol ratio of m-phthalic acid and terephthalic acid is 0.2, polymerizing catalyst is antimony acetate, and consumption is 200 grams. Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97% to esterification yield, obtain esterification material in esterification reaction process.
Then, being 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk reaction period, reaction pressure is evacuated down to 600Pa gradually from normal atmosphere.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the temperature of reaction polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester limiting viscosity and fusing point
For ease of comparing, limiting viscosity and fusing point are arranged in table 1.
3, plate property test
For ease of comparing, the performance of sheet material is arranged in table 2.
4, plastics sucking moulding test
Prepared sheet material is used for the test of case and bag plastics sucking moulding, test-results is arranged in table 3.
[embodiment 3]
1, the preparation of modified poly ester
The reactor of 1000 liters adds esterification raw material and polymerizing catalyst. Wherein esterification raw material is terephthalic acid, m-phthalic acid, ethylene glycol, tetramethylolmethane and pyromellitic acid anhydride, esterification raw material gross weight 400 kilograms, taking molar ratio computing (terephthalic acid+m-phthalic acid): ethylene glycol: tetramethylolmethane: pyromellitic acid anhydride is as 1:1.2:0.0015:0.0015, the mol ratio of m-phthalic acid and terephthalic acid is 0.2, polymerizing catalyst is antimony acetate, and consumption is 200 grams. Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97% to esterification yield, obtain esterification material in esterification reaction process.
Then, being 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk reaction period, reaction pressure is evacuated down to 600Pa gradually from normal atmosphere.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the temperature of reaction polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester limiting viscosity and fusing point
For ease of comparing, limiting viscosity and fusing point are arranged in table 1.
3, plate property test
For ease of comparing, the performance of sheet material is arranged in table 2.
4, plastics sucking moulding test
Prepared sheet material is used for the test of case and bag plastics sucking moulding, test-results is arranged in table 3.
From the plastics sucking moulding test-results of embodiment 3 and embodiment 1 and embodiment 2 it may be seen that tetramethylolmethane and pyromellitic acid anhydride reducing be full of cracks, hang stream or in the probability that turns white, there is obvious synergy.
[embodiment 4]
1, the preparation of modified poly ester
The reactor of 1000 liters adds esterification raw material and polymerizing catalyst. Wherein esterification raw material is terephthalic acid, m-phthalic acid, ethylene glycol, tetramethylolmethane and pyromellitic acid anhydride, esterification raw material gross weight 400 kilograms, taking molar ratio computing (terephthalic acid+m-phthalic acid): ethylene glycol: tetramethylolmethane: pyromellitic acid anhydride is as 1:1.2:0.0015:0.0015, the mol ratio of m-phthalic acid and terephthalic acid is 0.2, polymerizing catalyst is antimony acetate, and consumption is 200 grams. Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97% to esterification yield, obtain esterification material in esterification reaction process.
Then, being 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk reaction period, reaction pressure is evacuated down to 600Pa gradually from normal atmosphere.
Finally, within .0 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the temperature of reaction polymerase 17 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester limiting viscosity and fusing point
For ease of comparing, limiting viscosity and fusing point are arranged in table 1.
3, plate property test
For ease of comparing, the performance of sheet material is arranged in table 2.
4, plastics sucking moulding test
Prepared sheet material is used for the test of case and bag plastics sucking moulding, test-results is arranged in table 3.
From embodiment 4 and embodiment 3 on year-on-year basis it may be seen that polyreaction reaches 3.5 hours polyreactions carries out very abundant, then it is less on the performance impact of product to extend polyreaction.
[comparative example 2]
It is that linking agent adds after polymerization procedure with embodiment 3 key distinction, specific as follows:
1, the preparation of polyester
The reactor of 1000 liters adds esterification raw material and polymerizing catalyst. Wherein esterification raw material is terephthalic acid, m-phthalic acid and ethylene glycol, esterification raw material gross weight 400 kilograms, taking molar ratio computing (terephthalic acid+m-phthalic acid): ethylene glycol is as 1:1.2, the mol ratio of m-phthalic acid and terephthalic acid is 0.2, polymerizing catalyst is antimony acetate, and consumption is 200 grams. Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97% to esterification yield, obtain esterification material in esterification reaction process.
Then, being 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk reaction period, reaction pressure is evacuated down to 600Pa gradually from normal atmosphere.
Finally, at temperature of reaction polyase 13 .5 hour of the reaction pressure of 80Pa and 285 DEG C, add tetramethylolmethane and the pyromellitic acid anhydride of respective amount in the esterification raw material with embodiment 3, continue temperature of reaction polyase 13 .5 hour the reaction pressure of 80Pa and 285 DEG C, water-cooled is cut into slices, and adds the Modified polyester chips of linking agent after obtaining.
2, the mensuration of modified poly ester limiting viscosity and fusing point
For ease of comparing, limiting viscosity and fusing point are arranged in table 1.
3, plate property test
For ease of comparing, the performance of sheet material is arranged in table 2.
4, plastics sucking moulding test
Prepared sheet material is used for the test of case and bag plastics sucking moulding, test-results is arranged in table 3.
By the data of comparative example in table 32 with embodiment 3 or embodiment 4 are compared and can find out, the modified poly ester of the present invention owing to adding linking agent in esterification raw material, inhale mould processing characteristics be far superior to adopt after polyreaction has completed or substantially completed, with linking agent, polyester is carried out modification again.
[embodiment 5]
1, the preparation of modified poly ester
It is to replace m-phthalic acid with hexanodioic acid with the key distinction of embodiment 3, it is specially:
The reactor of 1000 liters adds esterification raw material and polymerizing catalyst. Wherein esterification raw material is terephthalic acid, hexanodioic acid, ethylene glycol, tetramethylolmethane and pyromellitic acid anhydride, esterification raw material gross weight 400 kilograms, taking molar ratio computing (terephthalic acid+hexanodioic acid): ethylene glycol: tetramethylolmethane: pyromellitic acid anhydride is as 1:1.2:0.0015:0.0015, the mol ratio of hexanodioic acid and terephthalic acid is 0.2, polymerizing catalyst is antimony acetate, and consumption is 200 grams. Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97% to esterification yield, obtain esterification material in esterification reaction process.
Then, being 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk reaction period, reaction pressure is evacuated down to 600Pa gradually from normal atmosphere.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the temperature of reaction polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester limiting viscosity and fusing point
For ease of comparing, limiting viscosity and fusing point are arranged in table 1.
3, plate property test
For ease of comparing, the performance of sheet material is arranged in table 2.
4, plastics sucking moulding test
Prepared sheet material is used for the test of case and bag plastics sucking moulding, test-results is arranged in table 3.
[embodiment 6]
1, the preparation of modified poly ester
Being with embodiment 3 key distinction, the diacid properties-correcting agent of embodiment 3 only adopts m-phthalic acid, and the diacid properties-correcting agent that the present embodiment adopts is m-phthalic acid and hexanodioic acid, is specially:
The reactor of 1000 liters adds esterification raw material and polymerizing catalyst. Wherein esterification raw material is terephthalic acid, m-phthalic acid, hexanodioic acid, ethylene glycol, tetramethylolmethane and pyromellitic acid anhydride, esterification raw material gross weight 400 kilograms, taking molar ratio computing (terephthalic acid+m-phthalic acid+hexanodioic acid): ethylene glycol: tetramethylolmethane: pyromellitic acid anhydride is as 1:1.2:0.0015:0.0015, (m-phthalic acid+hexanodioic acid): the mol ratio of terephthalic acid is 0.2, m-phthalic acid: hexanodioic acid mol ratio is 1; Polymerizing catalyst is antimony acetate, and consumption is 200 grams. Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97% to esterification yield, obtain esterification material in esterification reaction process.
Then, being 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk reaction period, reaction pressure is evacuated down to 600Pa gradually from normal atmosphere.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the temperature of reaction polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester limiting viscosity and fusing point
For ease of comparing, limiting viscosity and fusing point are arranged in table 1.
3, plate property test
For ease of comparing, the performance of sheet material is arranged in table 2.
4, plastics sucking moulding test
Prepared sheet material is used for the test of case and bag plastics sucking moulding, test-results is arranged in table 3.
As can be seen from embodiment 6 and embodiment 5 and embodiment 1 are on year-on-year basis, m-phthalic acid and hexanodioic acid are moulded in processing characteristics in the suction improving modified poly ester, there is the interaction being better than simple superposition, it is embodied in both and is reducing be full of cracks, hang stream and in the probability occurred that turns white, there is synergy.
[embodiment 7]
1, the preparation of modified poly ester
It is with the key distinction of embodiment 6 to additionally use neopentyl glycol as glycol modification agent, it is specially:
The reactor of 1000 liters adds esterification raw material and polymerizing catalyst. Wherein esterification raw material is terephthalic acid, m-phthalic acid, hexanodioic acid, ethylene glycol, neopentyl glycol, tetramethylolmethane and pyromellitic acid anhydride, esterification raw material gross weight 400 kilograms, taking molar ratio computing (terephthalic acid+m-phthalic acid+hexanodioic acid): (ethylene glycol+neopentyl glycol): tetramethylolmethane: pyromellitic acid anhydride is as 1:1.2:0.0015:0.0015, (m-phthalic acid+hexanodioic acid): the mol ratio of terephthalic acid is 0.2, m-phthalic acid: hexanodioic acid mol ratio is 1, neopentyl glycol: ethylene glycol mol ratio is 0.2; Polymerizing catalyst is antimony acetate, and consumption is 200 grams. Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97% to esterification yield, obtain esterification material in esterification reaction process.
Then, being 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk reaction period, reaction pressure is evacuated down to 600Pa gradually from normal atmosphere.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the temperature of reaction polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester limiting viscosity and fusing point
For ease of comparing, limiting viscosity and fusing point are arranged in table 1.
3, plate property test
For ease of comparing, the performance of sheet material is arranged in table 2.
4, plastics sucking moulding test
Prepared sheet material is used for the test of case and bag plastics sucking moulding, test-results is arranged in table 3.
[embodiment 8]
1, the preparation of modified poly ester
It is with the key distinction of embodiment 7 to adopt 1,4-butyleneglycol to replace neopentyl glycol as glycol modification agent, it is specially:
The reactor of 1000 liters adds esterification raw material and polymerizing catalyst. Wherein esterification raw material is terephthalic acid, m-phthalic acid, hexanodioic acid, ethylene glycol, 1,4-butyleneglycol, tetramethylolmethane and pyromellitic acid anhydride, esterification raw material gross weight 400 kilograms, with molar ratio computing (terephthalic acid+m-phthalic acid+hexanodioic acid): (ethylene glycol+1,4-butyleneglycol): tetramethylolmethane: pyromellitic acid anhydride is 1:1.2:0.0015:0.0015, (m-phthalic acid+hexanodioic acid): the mol ratio of terephthalic acid is 0.2, m-phthalic acid: hexanodioic acid mol ratio is 1,1,4-butyleneglycol: ethylene glycol mol ratio is 0.2; Polymerizing catalyst is antimony acetate, and consumption is 200 grams. Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97% to esterification yield, obtain esterification material in esterification reaction process.
Then, being 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk reaction period, reaction pressure is evacuated down to 600Pa gradually from normal atmosphere.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the temperature of reaction polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester limiting viscosity and fusing point
For ease of comparing, limiting viscosity and fusing point are arranged in table 1.
3, plate property test
For ease of comparing, the performance of sheet material is arranged in table 2.
4, plastics sucking moulding test
Prepared sheet material is used for the test of case and bag plastics sucking moulding, test-results is arranged in table 3.
[embodiment 9]
1, the preparation of modified poly ester
Being with the key distinction of embodiment 7, the present embodiment adopts 1,4-butyleneglycol and neopentyl glycol as glycol modification agent simultaneously, is specially:
The reactor of 1000 liters adds esterification raw material and polymerizing catalyst. wherein esterification raw material is terephthalic acid, m-phthalic acid, hexanodioic acid, ethylene glycol, 1, 4-butyleneglycol, neopentyl glycol, tetramethylolmethane and pyromellitic acid anhydride, esterification raw material gross weight 400 kilograms, with molar ratio computing (terephthalic acid+m-phthalic acid+hexanodioic acid): (ethylene glycol+1, 4-butyleneglycol+neopentyl glycol): tetramethylolmethane: pyromellitic acid anhydride is 1:1.2:0.0015:0.0015, (m-phthalic acid+hexanodioic acid): the mol ratio of terephthalic acid is 0.2, m-phthalic acid: hexanodioic acid mol ratio is 1, (1, 4-butyleneglycol+neopentyl glycol): ethylene glycol mol ratio is 0.2, 1, 4-butyleneglycol: neopentyl glycol mol ratio is 1, polymerizing catalyst is antimony acetate, and consumption is 200 grams. making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97% to esterification yield, obtain esterification material in esterification reaction process.
Then, being 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk reaction period, reaction pressure is evacuated down to 600Pa gradually from normal atmosphere.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the temperature of reaction polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester limiting viscosity and fusing point
For ease of comparing, limiting viscosity and fusing point are arranged in table 1.
3, plate property test
For ease of comparing, the performance of sheet material is arranged in table 2.
4, plastics sucking moulding test
Prepared sheet material is used for the test of case and bag plastics sucking moulding, test-results is arranged in table 3.
From embodiment 9 and embodiment 7 and embodiment 8 on year-on-year basis, mould in processing characteristics in the suction improving modified poly ester of the present invention, 1,4-butyleneglycol and neopentyl glycol have useful synergy, and both hang in reduction in the probability flowing and turning white and have synergy more specifically.
The feature viscosity of table 1 modified poly ester and fusing point
| Limiting viscosity, dl/g | Fusing point, DEG C | |
| Embodiment 1 | 0.7520 | 202 |
| Comparative example 1 | 0.7625 | 204 |
| Embodiment 2 | 0.7590 | 206 |
| Embodiment 3 | 0.7612 | 200 |
| Embodiment 4 | 0.7710 | 198 |
| Comparative example 2 | 0.7595 | 198 |
| Embodiment 5 | 0.8637 | 205 |
| Embodiment 6 | 0.7625 | 210 |
| Embodiment 7 | 0.7514 | 215 |
| Embodiment 8 | 0.7692 | 220 |
| Embodiment 9 | 0.7533 | 225 |
The performance of table 2 sheet material
Table 3 is inhaled and is moulded processing characteristics
| Blow quick-fried | Be full of cracks | Hang stream | Turn white | |
| Embodiment 1 | Better | Poor | Poor | Worst |
| Comparative example 1 | Worst | Worst | Worst | Worst |
| Embodiment 2 | Better | Poor | Worst | Poor |
| Embodiment 3 | Better | Better | Better | Poor |
| Embodiment 4 | Better | Better | Better | Poor |
| Comparative example 2 | Poor | Worst | Worst | Worst |
| Embodiment 5 | Better | Poor | Better | Poor |
| Embodiment 6 | Better | Better | Better | Better |
| Embodiment 7 | Best | Best | Best | Better |
| Embodiment 8 | Best | Best | Better | Better |
| Embodiment 9 | Best | Best | Best | Best |
Claims (5)
1. a modified poly ester, limiting viscosity is 0.7��1.4dl/g, and fusing point is 170 ~ 240 DEG C, adopts and comprises the reaction raw materials copolymerization of linking agent, properties-correcting agent, terephthalic acid and ethylene glycol and obtain; The molecule of described linking agent has the functional group that can form at most 3 or more than 3 crosslinked links in described modified poly ester; Described linking agent comprises polyvalent alcohol and polyprotonic acid simultaneously, or described linking agent comprises the acid anhydrides of polyvalent alcohol and polyprotonic acid simultaneously; Described properties-correcting agent is selected from diacid properties-correcting agent and/or glycol modification agent, has 2 hydroxy-acid groups in described diacid modifier molecules, has 2 alcohol hydroxyls in described glycol modification agent molecule; Taking molar ratio computing (terephthalic acid+diacid properties-correcting agent): (ethylene glycol+glycol modification agent): linking agent is as 1:(1.1��2.0): (0.001��0.005), the mol ratio of diacid properties-correcting agent and terephthalic acid is a, and the mol ratio of glycol modification agent and ethylene glycol is b; A+b=0.10 ~ 0.45; Described many units are 3 yuan or more than 3 yuan;
At least one that described polyvalent alcohol is selected from tetramethylolmethane, dipentaerythritol, tripentaerythritol, TriMethylolPropane(TMP), trimethylolethane and glycerine;
The acid anhydrides of described polyprotonic acid is pyromellitic acid anhydride;
Described diacid properties-correcting agent is m-phthalic acid and/or hexanodioic acid;
Described glycol modification agent is neopentyl glycol and/or 1,4-butyleneglycol;
At least one that described polyprotonic acid is selected from trimesic acid and Pyromellitic Acid.
2. the preparation method of modified poly ester described in claim 1, comprises the steps:
(1) make described reaction raw materials carry out esterification and obtain carboxylate;
(2) precondensation;
(3) polycondensation.
3. the preparation method of modified poly ester according to claim 2, is characterized in that the temperature of described esterification is 240��280 DEG C.
4. preparation method according to claim 2, is characterized in that the temperature of described polycondensation is 270��290 DEG C.
5. modified poly ester described in claim 1 is in the application produced in case board.
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| CN111154080B (en) * | 2020-01-19 | 2022-07-05 | 万凯新材料股份有限公司 | Extrusion blow-molded PET resin and preparation method thereof |
| CN111454438B (en) * | 2020-05-15 | 2022-08-02 | 河北华密新材科技股份有限公司 | Modified PET resin and preparation method thereof |
| CN112979931A (en) * | 2021-04-26 | 2021-06-18 | 四川大学 | Transparent degradable copolyester and preparation method thereof |
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| CN102206331A (en) * | 2010-03-30 | 2011-10-05 | 中国石油化工股份有限公司 | Polyester and method for preparing film by using polyester |
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