CN109776772B - Polyester, preparation method and thermoplastic vulcanized rubber - Google Patents
Polyester, preparation method and thermoplastic vulcanized rubber Download PDFInfo
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- CN109776772B CN109776772B CN201711121261.9A CN201711121261A CN109776772B CN 109776772 B CN109776772 B CN 109776772B CN 201711121261 A CN201711121261 A CN 201711121261A CN 109776772 B CN109776772 B CN 109776772B
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Abstract
The invention discloses polyester, a preparation method and thermoplastic vulcanized rubber. Said poly(s)The ester is prepared from 1, 4-butanediol, succinic acid, 2, 3-butanediol, and itaconic acid; the structural formula is as follows:
the thermoplastic vulcanizate is obtained by dynamically vulcanizing raw materials comprising the following components: polyester PBBSI and polylactic acid; the mass ratio of the two is 60:40 to 80/20. The raw material source of the invention is simple, and the prepared thermoplastic vulcanized rubber can be subjected to 3D printing. The invention reduces the dependence on petroleum resources, and meanwhile, the material is degradable, nontoxic and more environment-friendly; and the preparation method is simple and is beneficial to industrial popularization and application. Meets the requirements of green chemical industry.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to polyester, a preparation method and thermoplastic vulcanized rubber.
Background
At present, 3D printing, in which the FDM method is commonly used, mainly uses thermoplastic plastics, such as: PLA, ABS, and the like. However, the hardness of the PLA material is high, the PLA material lacks toughness, the PLA material needs to be modified and applied to 3D printing, the toughness is improved by using a toughening mode, but the hardness of the PLA material is still high, and the requirements of printing products with flexible requirements cannot be met.
The current thermoplastic vulcanizate systems are numerous, for example: the ratio of 65/35 of butyl rubber (IIR) and nylon (PA12) is carried out in an open mill at 190 ℃ for 7min to obtain a premix, and then the premix is simply blended on the open mill and dynamically vulcanized to obtain a thermoplastic vulcanized rubber material; nitrile rubber NBR and nylon (PA6) system: plasticating NBR on a normal-temperature open mill, adding an anti-aging agent RD, and discharging rubber compound into sheets for later use; drying PA6 at 80 ℃ for 12 hours, melting PA6 at 230 ℃ on a high-temperature open mill, adding the prepared NBR rubber compound, adding heat-resistant oxidant 1010, uniformly mixing, and cooling to a normal-temperature open mill to obtain sheets; adding a vulcanizing agent and a vulcanizing aid on a normal-temperature open mill, uniformly mixing, and then taking out pieces to prepare a rubber-plastic premix; dynamically vulcanizing the rubber-plastic premix on a high-temperature open mill at 230 ℃ to obtain the material with uniform texture
Like the above materials, petroleum-based materials are prepared, which have great demand for petroleum resources and cause environmental pollution, and we hope to develop a novel green, environment-friendly and degradable material.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides polyester, a preparation method and thermoplastic vulcanizate. The material disclosed by the invention can be used for 3D printing, the dependence on petroleum resources is reduced, and meanwhile, the material is degradable and non-toxic.
One of the objects of the present invention is to provide a polyester.
The structural formula is as follows:
the invention also aims to provide a preparation method of the polyester.
The method comprises the following steps:
(1)1, 4-butanediol, succinic acid, 2, 3-butanediol and itaconic acid are mixed, added with a polymerization inhibitor accounting for 0.1 to 0.12 percent of the total mass of the four monomers and a catalyst TBT accounting for 0.1 to 0.15 percent of the total mass of the four monomers, placed in a three-neck flask, vacuumized to negative pressure, then returned to normal pressure by nitrogen, and repeatedly operated for three to five times;
the mass ratio of 1, 4-butanediol, 2, 3-butanediol, succinic acid and itaconic acid is (0.05-0.25): (0.25-0.45): (0.44-0.46): (0.04 to 0.06);
(2) heating to 160-170 ℃ for reaction for 2-3 hours, heating to 175-185 ℃ for reaction for 2-2.5 hours, reducing the temperature to 40-60 ℃, adding a catalyst TBT accounting for 0.1-0.15% of the total mass of the four monomers, raising the reaction temperature to 220-230 ℃ for reaction until a pole climbing phenomenon appears, and stopping the reaction to obtain the polyester PBBSI.
Wherein the content of the first and second substances,
the polymerization inhibitor is tris (4-hydroxy-TEMPO) phosphate.
The catalyst TBT is prepared from tetrabutyl titanate and methanol according to the mass ratio of 1: 10.
The reaction process is as follows:
it is a further object of the present invention to provide a thermoplastic vulcanizate.
The thermoplastic vulcanizate is obtained by dynamically vulcanizing raw materials comprising the following components:
polyester PBBSI and polylactic acid; the mass ratio of the two is 60:40 to 80/20; preferably 60/40 to 70/30.
The fourth purpose of the invention is to provide a preparation method of thermoplastic vulcanizate.
The method comprises the following steps:
and blending the polyester PBBSI and the polylactic acid according to the using amount, and dynamically vulcanizing to prepare the thermoplastic vulcanized rubber.
Among them, preferred are:
the blending temperature is 170-172 ℃; the blending time is 8-10 minutes;
the vulcanization temperature is 190-192 ℃; the vulcanization time is 10-15 minutes.
The method specifically comprises the following steps:
the synthesized polyester PBBSI and the purchased PLA are simply blended in a haake according to the mass ratio of 60:40, the using temperature is 170 ℃, the rotating speed is 80, the mixture is mixed for 8 to 10 minutes, then the mixture is taken on an open mill, 0.05 percent of the total mass of the mixture is added, after the multiple open milling is finished, the mixture is placed in the haake at 190 ℃ for dynamic vulcanization, the rotating speed is 80, and the vulcanization is finished in about 10 minutes.
The fifth purpose of the invention is to provide an application of thermoplastic vulcanizate in 3D printing.
The thermoplastic vulcanized rubber can be subjected to 3D printing, and the printing effect is good.
The invention has the following effects:
the raw material source of the invention is simple, and the prepared thermoplastic vulcanized rubber can be subjected to 3D printing. The invention reduces the dependence on petroleum resources, and meanwhile, the material is degradable, nontoxic and more environment-friendly; and the preparation method is simple and is beneficial to industrial popularization and application. Meets the requirements of green chemical industry.
Drawings
FIG. 1 is an infrared spectrum diagram of polyester PBBSI with different component ratios
FIG. 2 is a nuclear magnetic structure spectrum of polyester with different component ratios
FIG. 3 capillary rheology of thermoplastic vulcanizate at different temperatures
4-Electron microscopy pictures on a 110 μm scale;
FIG. 4-Electron microscope pictures on a 230 μm scale
4-320 μm;
FIGS. 4-450 μm scale electron microscope pictures.
Detailed Description
The present invention will be further described with reference to the following examples.
The raw materials except the catalyst are all sold in the market;
self-making a catalyst TBT: preparing tetrabutyl titanate and methanol according to the mass ratio of 1: 10;
example 1:
reacting 1, 4-butanediol, 2, 3-butanediol, succinic acid and itaconic acid according to the proportion of 0.25/0.25/0.45/0.05, adding a polymerization inhibitor 705 (tris (4-hydroxy-TEMPO) phosphate) accounting for 0.1 percent of the total mass, placing a catalyst TBT accounting for 0.1 percent of the total mass of the system into a three-neck flask, vacuumizing to negative pressure, introducing nitrogen to return to normal pressure, and repeatedly operating for three to five times; heating to 160 ℃ for reaction for 2 hours, heating to 180 ℃ for reaction for 2 hours, reducing the temperature to 40 ℃, adding 0.1% of catalyst TBT (tert-butyl titanate) in the total mass, increasing the reaction temperature to 220 ℃ for reaction until a pole climbing phenomenon appears, and stopping the reaction to obtain polyester PBBSI, wherein the infrared performance characterization is that PBBSI-50 in figure 1 and the nuclear magnetic performance characterization is a PBBSI-50 curve in figure 2;
the synthesized polyester PBBSI and PLA are simply blended in a haake according to the mass ratio of 60:40, the using temperature is 170 ℃, the rotating speed is 80r, the mixture is mixed for 8 to 10 minutes, then the mixture is taken on an open mill, 0.05 part of DCP (dicumyl peroxide) accounting for 60 percent of the total mass of the mixture is added, after the mixture is milled for a plurality of times, the mixture is dynamically vulcanized in the haake at 190 ℃, the rotating speed is 80r, and the vulcanization is finished in about 10 to 15 minutes. And then the three-dimensional flower is applied to 3D printing, and the three-dimensional flower is printed at the temperature of 200 ℃.
Example 2:
reacting 1, 4-butanediol, 2, 3-butanediol, succinic acid and itaconic acid according to the proportion of 0.15/0.35/0.45/0.05, adding a polymerization inhibitor 705 (tris (4-hydroxy-TEMPO) phosphate) accounting for 0.11 percent of the total mass, placing a catalyst TBT accounting for 0.13 percent of the total mass of the system into a three-neck flask, vacuumizing to negative pressure, returning nitrogen to normal pressure, and repeatedly operating for three to five times; heating to 160 ℃ for reaction for 2 hours, heating to 180 ℃ for reaction for 2 hours, reducing the temperature to 40 ℃, adding 0.13% of catalyst TBT (tert-butyl titanate) in the total mass, increasing the reaction temperature to 220 ℃ for reaction until a pole climbing phenomenon appears, and stopping the reaction to obtain polyester PBBSI, wherein the infrared performance characterization is that PBBSI-70 in figure 1 and the nuclear magnetic performance characterization is a PBBSI-70 curve in figure 2;
the synthesized polyester PBBSI and the purchased PLA are simply blended in a haake according to the mass ratio of 60:40, the using temperature is 171 ℃, the rotating speed is 80r, the mixture is mixed for 8 to 10 minutes, then the mixture is taken on an open mill, 0.05 part of DCP (dicumyl peroxide) accounting for 60 percent of the total mass of the mixture is added, after the mixture is opened for a plurality of times, the mixture is dynamically vulcanized in the haake at 190 ℃, the rotating speed is 80r, and the vulcanization is finished for about 10 to 15 minutes. For the atomic force electron microscope analysis, as shown in fig. 4, observation under four different scales shows that all the structures are sea-island structures, the phase inversion of dynamic vulcanization is completed, and the preparation of TPV is realized. And then the product is applied to 3D printing, and the product tensile sample strip is printed by printing at the temperature of 200 ℃.
Example 3:
reacting 1, 4-butanediol, 2, 3-butanediol, succinic acid and itaconic acid according to the proportion of 0.05/0.45/0.45/0.05, adding a polymerization inhibitor 705 (tris (4-hydroxy-TEMPO) phosphate) accounting for 0.12 percent of the total mass, placing a catalyst TBT accounting for 0.15 percent of the total mass of the system into a three-neck flask, vacuumizing to negative pressure, returning nitrogen to normal pressure, and repeatedly operating for three to five times; heating to 160 ℃ for reaction for 2 hours, heating to 180 ℃ for reaction for 2 hours, reducing the temperature to 40 ℃, adding 0.15% of catalyst TBT (tert-butyl titanate) in the total mass, increasing the reaction temperature to 220 ℃ for reaction until a pole climbing phenomenon appears, and stopping the reaction to obtain polyester PBBSI, wherein the infrared performance characterization is that PBBSI-90 in figure 1 and the nuclear magnetic performance characterization is that a PBBSI-90 curve in figure 2;
the synthesized polyester PBBSI and the purchased PLA are simply blended in a haake according to the mass ratio of 60:40, the using temperature is 172 ℃, the rotating speed is 80r, the mixture is mixed for 8 to 10 minutes, then the mixture is taken on an open mill, 0.05 part of DCP (dicumyl peroxide) accounting for 60 percent of the total mass of the mixture is added, after the mixture is opened for a plurality of times, the mixture is dynamically vulcanized in the haake at 190 ℃, the rotating speed is 80r, and the vulcanization is finished for about 10 to 15 minutes. And then the product is applied to 3D printing, and the product tensile sample strip is printed by printing at the temperature of 200 ℃.
Example 4:
the difference is only that the formula of the polyester synthesis is different from that of the example 1; 1, 4-butanediol, 2, 3-butanediol, succinic acid and itaconic acid react according to the proportion of 0.20/0.30/0.45/0.05. The other steps operate the same. The infrared characterization is the curve PBBSI-60 in FIG. 1, and the nuclear magnetism characterization is the curve PBBSI-60 in FIG. 2.
Example 5:
the difference is only that the formula of the polyester synthesis is different from that of the example 1; 1, 4-butanediol, 2, 3-butanediol, succinic acid and itaconic acid react according to the proportion of 0.10/0.40/0.45/0.05. The other steps operate the same. The infrared characterization is the curve PBBSI-80 in FIG. 1, and the nuclear magnetism characterization is the curve PBBSI-80 in FIG. 2.
As shown in fig. 1: the infrared spectrum of the polyester is taken as an example along with the change of the content of the 2, 3-butanediol, and the absorption peaks of 2935cm-1 and 2854cm-1 represent the characteristic absorption peaks of methylene; the 1731cm-1 absorption peak represents an ester carbonyl stretching vibration peak, and the 1160cm-1 absorption peak represents an ester bond stretching vibration peak of C-O-C ═ O, and the two absorption peaks indicate the existence of an ester bond. The absorption peak at 807cm-1 of the fingerprint region represents the double bond of itaconic acid, which represents the successful incorporation of itaconic acid into the copolyester.
As shown in fig. 2: analyzing a nuclear magnetic spectrum, wherein characteristic groups in the polymer are consistent with peak positions in the nuclear magnetic spectrum, and the chemical shift of methylene in-CH 2-COO-of 1, 4-succinic acid is 2.64 ppm. The proton signal of-CO-CH 2-CH 2-in 1, 4-butanediol is at the position of 4.15,1.73 ppm. The peaks at 1.23ppm and 5.01ppm characterize the oscillation of the methylene and side methyl groups of-O-CH (CH3), respectively, in 2, 3-butanediol and also confirm the successful incorporation of 2, 3-butanediol into the polymer. Chemical shifts at 6.35ppm, 5.73ppm and 3.36ppm showed characteristic peaks for the pendant alkenyl and methylene groups in-CO-C (═ CH2) -CH2 of IA. Referring to FIGS. 2-3(b), for the copolyesters PBBSI with different 2, 3-butanediol contents, the peak area increases with the increase of the 2, 3-butanediol content, while the peak at 5.01ppm increases, and the peak at 4.15ppm decreases gradually, and the peak area decreases, which is consistent with the change rule of the 2, 3-butanediol content.
As shown in fig. 3: the rheological property analysis of the PBBSI/PLA TPV material at 190 ℃, 200 ℃ and 210 ℃ shows that the shear rate is increased and the shear viscosity is gradually reduced at a certain temperature, namely the phenomenon of typical shear thinning. At the same shear rate, the temperature increases and the shear viscosity becomes smaller.
In the atomic force spectrum (as shown in fig. 4-1,4-2,4-3,4-4), the particle distribution morphology of the PBBSI polyester and PLA is analyzed by using different scales respectively, and the phase inversion is completed after the dispersion of the PBBSI polyester and the PLA is simply blended, vulcanized by a cold roll and dynamically vulcanized, so that the thermoplastic vulcanizate conforms to the 'sea-island structure'.
Claims (7)
1. A polyester PBBSI characterized by:
the polyester PBBSI is prepared from 1, 4-butanediol, succinic acid, 2, 3-butanediol and itaconic acid;
the structural formula is as follows:
the polyester PBBSI is prepared by a method comprising the following steps:
(1)1, 4-butanediol, 2, 3-butanediol, succinic acid and itaconic acid are mixed, added with a polymerization inhibitor accounting for 0.1 to 0.12 percent of the total mass of the four monomers and a catalyst TBT accounting for 0.1 to 0.15 percent of the total mass of the four monomers, placed in a three-neck flask, vacuumized to negative pressure, then returned to normal pressure by nitrogen, and repeatedly operated for three to five times;
the mass ratio of 1, 4-butanediol, 2, 3-butanediol, succinic acid and itaconic acid is (0.05-0.25): (0.25-0.45): (0.44-0.46): (0.04 to 0.06);
(2) heating to 160-170 ℃ for reaction for 2-3 hours, heating to 175-185 ℃ for reaction for 2-2.5 hours, reducing the temperature to 40-60 ℃, adding a catalyst TBT (tert-butyl terephthalate) accounting for 0.1-0.15% of the total mass of the four monomers, heating to 220-230 ℃ for reaction until a pole climbing phenomenon appears, and stopping the reaction to obtain polyester PBBSI;
the polymerization inhibitor is tris (4-hydroxy-TEMPO) phosphate;
the catalyst TBT is prepared from tetrabutyl titanate and methanol according to the mass ratio of 1: 10.
2. A process for the preparation of the polyester PBBSI as claimed in claim 1, characterized in that the process comprises:
(1)1, 4-butanediol, 2, 3-butanediol, succinic acid and itaconic acid are mixed, added with a polymerization inhibitor accounting for 0.1 to 0.12 percent of the total mass of the four monomers and a catalyst TBT accounting for 0.1 to 0.15 percent of the total mass of the four monomers, placed in a three-neck flask, vacuumized to negative pressure, then returned to normal pressure by nitrogen, and repeatedly operated for three to five times;
the mass ratio of 1, 4-butanediol, 2, 3-butanediol, succinic acid and itaconic acid is (0.05-0.25): (0.25-0.45): (0.44-0.46): (0.04 to 0.06);
(2) heating to 160-170 ℃ for reaction for 2-3 hours, heating to 175-185 ℃ for reaction for 2-2.5 hours, reducing the temperature to 40-60 ℃, adding a catalyst TBT (tert-butyl terephthalate) accounting for 0.1-0.15% of the total mass of the four monomers, heating to 220-230 ℃ for reaction until a pole climbing phenomenon appears, and stopping the reaction to obtain polyester PBBSI;
the polymerization inhibitor is tris (4-hydroxy-TEMPO) phosphate;
the catalyst TBT is prepared from tetrabutyl titanate and methanol according to the mass ratio of 1: 10.
3. A thermoplastic vulcanizate prepared with the polyester PBBSI of claim 1, characterized in that the thermoplastic vulcanizate is obtained by dynamic vulcanization of raw materials comprising:
polyester PBBSI and polylactic acid; the mass ratio of the two is 60:40 to 80/20.
4. The thermoplastic vulcanizate of claim 3, wherein:
polyester PBBSI and polylactic acid; the mass ratio of the two is 60/40 to 70/30.
5. A process for the preparation of a thermoplastic vulcanizate according to any of claims 3 to 4, characterized in that the process comprises:
and blending the polyester PBBSI and the polylactic acid according to the using amount, and dynamically vulcanizing to prepare the thermoplastic vulcanized rubber.
6. The process for preparing a thermoplastic vulcanizate according to claim 5, wherein:
the blending temperature is 170-172 ℃; the blending time is 8-10 minutes;
the vulcanization temperature is 190-192 ℃; the vulcanization time is 10-15 minutes.
7. Use of a thermoplastic vulcanizate according to any one of claims 3 to 4 in 3D printing.
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| JP2010265352A (en) * | 2009-05-13 | 2010-11-25 | Hitachi Plant Technologies Ltd | Method and apparatus for producing polyester |
| CN102827465B (en) * | 2012-07-27 | 2014-08-20 | 北京化工大学 | Degradable biobased thermoplastic vulcanized rubber |
| CN103012818B (en) * | 2012-12-21 | 2014-07-09 | 青岛科技大学 | Bio-based vulcanization polyester rubber particle and preparation method thereof |
| CN104017339A (en) * | 2014-06-17 | 2014-09-03 | 四川大学 | High-toughness polylactic acid alloy and preparation method thereof |
| CN105670252B (en) * | 2016-02-02 | 2017-11-17 | 青岛科技大学 | A kind of plasticizing polylactic acid composition and preparation method thereof |
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