CN106750266B - A kind of continuous polymerization technique and PA6-6X copolymer of PA6-6X copolymer - Google Patents
A kind of continuous polymerization technique and PA6-6X copolymer of PA6-6X copolymer Download PDFInfo
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- CN106750266B CN106750266B CN201611013520.1A CN201611013520A CN106750266B CN 106750266 B CN106750266 B CN 106750266B CN 201611013520 A CN201611013520 A CN 201611013520A CN 106750266 B CN106750266 B CN 106750266B
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- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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Abstract
The invention discloses a kind of continuous polymerization technique of PA6-6X copolymer and PA6-6X copolymers, belong to nylon technical field.In PA6-6X copolymer, the mass percentage of PA6X salt reaches as high as 60%, and copolymer fusing point is between 158.5 DEG C -218.8 DEG C, and relative viscosity is between 2.4-3.6.PA6-6X copolymer is prepared using three-stage continuous polymerization, it is characterized in that the addition manner combined using solid nylon 6X salt and nylon 6X saline solution, it is uniformly mixed caprolactam before the reaction with 6X salt, the random copolymer of height is obtained by polymerization, when preparing PA6-6X copolymer using the preparation method, process operability is strong.PA6-6X copolymer obtained has low fusing point, broader process window, is suitble to the application such as extrusion, inflation film and hot melt adhesive.
Description
Technical field
The present invention relates to technical field of chemical synthesis, a kind of continuous polymerization technique more particularly to PA6-6X copolymer and
PA6-6X copolymer.
Background technique
Nylon 6 has excellent physical and mechanical property, good wearability, excellent oil resistant, solvent resistant, corrosion resistance
Can, it is widely used the advantages that but also with self-lubrication and good processing performance, but there are dry state or low temperature undershoots for nylon 6
The disadvantages of hit intensity is low, transparent poor, fusing point is poor compared with flexibility under high and low temperature, limits its application.To expand answering for nylon 6
With range, meeting the needs of more areas, people are modified nylon 6, and wherein modification by copolymerization has the characteristics that excellent effect,
It quickly grows.
Nylon 610,612 comprehensive performance have stronger rigidity and resistance to close to long carbon chain nylon, but than long carbon chain nylon
It is hot, such as intensity and heat resistance be higher than nylon 1212 long carbon chain nylon, and flexibility, the transparency, low-temperature impact-resistant performance
It is better than the short carbon chains nylon such as nylon 6.Early stage nylon 610,612 synthesis using ethyl alcohol as solvent, due to the inflammable and explosive presence of ethyl alcohol
Security risk.In addition, being used as block since prepolymer has been formed via the diamines of low molecular weight condensation and the block of dicarboxylic acids
Then with remain on holding in the polymerizeing of caprolactam, the more preferable random distribution of component will not occur, need more diamines
The salt formed with dicarboxylic acids is to reach required copolymer fusing point.
Summary of the invention
In view of this, the present invention provides a kind of continuous polymerization technique of PA6-6X copolymer and PA6-6X copolymer, it should
Monomeric unit has better random distribution in copolymer, lower fusing point is shown, thus more suitable for practical.
In order to reach above-mentioned first purpose, the continuous polymerization technique and PA6-6X of PA6-6X copolymer provided by the invention
The technical solution of copolymer is as follows:
The continuous polymerization technique and PA6-6X copolymer of PA6-6X copolymer provided by the invention are polymerize using three-stage, are made
With caprolactam (CPL) and nylon 6X salt, i.e. mixing produces PA6-6X copolymerization subsequently into high-temperature high-voltage reaction device before the reaction
Object, comprising the following steps:
1) it is mixed to get mixture I in mixed flow container using caprolactam and solid nylon 6X salt, by mixture I, nylon
6X saline solution mixes in pipe-line mixer；
2) material that step 1) mixes is sent to first reactor to polymerize to form prepolymer；
3) material after first reactor is sent to the first amide exchanger, and the material after the first amide exchanger is sent to second
Reactor；
4) material for obtaining step 3) is sent to the second amide exchanger, and the material after the second amide exchanger is sent to third
Reactor；
5) the PA6-6X Copolymer Melts for obtaining step 4) carry out pelletizing by pelleter, then using extraction, dry
PA6-6X copolymer slice finished product is obtained after dry.
Following technology also can be used in the continuous polymerization technique and PA6-6X copolymer of PA6-6X copolymer provided by the invention
Measure further realizes.
Preferably, raw material is grouped as by each group of following weight parts: mass content be 70-99.8% caprolactam,
The auxiliary agent that 6X salt that mass content is 0.2-30%, mass content are 0.02-0.5%.
Preferably, raw material is grouped as by each group of following weight parts: mass content is the caprolactam of 40-70%, matter
Measure content be 30-60% 6X salt, mass content be 0.02-0.5% auxiliary agent.
Preferably, the caprolactam is fresh caprolactam or fresh caprolactam and the caprolactam by recycling
Mixture.
Preferably, fresh caprolactam in the mixture of the fresh caprolactam and the caprolactam by recycling
Mass content is not less than 50%.
Preferably, the nylon 6X salt is nylon 612 salt or nylon 610 salt.
Preferably, the amount of the solid nylon 6X salt is calculated as 0.2-30% based on the total amount of monomer.
Preferably, the preparation method of the mixture I is in the case where purity is greater than 99.999% nitrogen atmosphere, using physics
Shearing dispersion or stirring or mixed allocation or the method for grinding obtain suspension or solution of the partial size less than 1 μm, the temperature
80-190 DEG C, time 30s-2h.
Preferably, the nylon 6X saline solution mass concentration is in 62%-80%.
Preferably, the nylon 6X saline solution mass concentration is in 62%-75%.
Preferably, the amount of 6X salt is calculated as 0-30% based on the total amount of monomer in the nylon 6X saline solution.
Preferably, the first reactor pressure 8-50bar, 245-285 DEG C of temperature, residence time 1-4h.
Preferably, the first reactor pressure 15-38bar, 260-280 DEG C of temperature, residence time 2-3h.
Preferably, the catalyst of amide exchange reaction is added or be not added to the step 1).
Preferably, the catalyst is shown in Formulas I and/or Formula II
R1-SO3-R2 I
Wherein R1Represent the alkyl group containing 1 to 16 carbon atom or phenyl or aminomethyl phenyl；R2Represent H, Li, Na
Or K；
R3-COO-M II
Wherein R3Represent H or the alkyl group containing 1 to 7 carbon atom；M represents Zn, Mg or Sn.
Preferably, the catalyst is p-methyl benzenesulfonic acid, paratoluenesulfonic acid sodium salt, p-methyl benzenesulfonic acid potassium, dodecyl sulphur
One or more of sour sodium, zinc acetate, magnesium acetate, stannous octoate.
Preferably, the conversion ratio of nylon 6X salt is in 90-98% in first reactor.
Preferably, the reactor comprising three non-duct types, and first and second and second with third reactor it
Between using draw ratio greater than 10,000 amide exchanger to strengthen amide exchange reaction.
Preferably, the first amide exchanger temperature control is at 245-285 DEG C, material is in the first amide exchanger
Residence time be 0.5-2h, pressure is down to 3-6bar from 8-50bar.
Preferably, the second reactor temperature control is at 255-275 DEG C, pressure is controlled in 3-6bar, and material stops
Staying the time is 2-3h.
Preferably, the third temperature of reactor control is at 240-255 DEG C, pressure is controlled in -50mbar~50mbar,
The residence time of material is 10-12h, nitrogen is led in the material on third reactor top, the consumption of the nitrogen is
0.1-1.5Nm3/ ton slice.
Preferably, using knockout tower or other types simultaneously in two reactor heads of second and third reactor
Technique the reactor head separate moisture.
The PA6-6X copolymer product fusing point is minimum up to 158.5 DEG C, and relative viscosity is between 2.4-3.6.
Compared with prior art, the continuous polymerization technique of PA6-6X copolymer provided by the invention and PA6-6X copolymer
It has the beneficial effect that
1. the addition manner for taking solid nylon 6X salt and nylon 6X saline solution to combine, 6X salt content can be up to
60%, it fully ensures that caprolactam, 6X salt, auxiliary agent etc. are uniformly mixed in molecular level, guarantees the stability and homogeneity of product.
2. promoting amide exchange reaction by addition catalyst, it is able to produce the PA6-6X copolymer of high degree of randomness.
3. technique solves excessive concentration when extract liquor is concentrated in current production technology and is easy what oligomer sedimentation generated
Line clogging problem, it is only necessary to using 69% concentrate, when greatly reducing concentration energy consumption and increase technique stability and
Operability.
4. three reactors in the present invention and two amide exchangers use different process parameter controls, technique can
Control property is strong.
Detailed description of the invention
By reading the following detailed description of the preferred embodiment, various other advantages and benefits are common for this field
Technical staff will become clear.The drawings are only for the purpose of illustrating a preferred embodiment, and is not considered as to the present invention
Limitation.And throughout the drawings, the same reference numbers will be used to refer to the same parts.In the accompanying drawings:
Fig. 1 is the continuous polymerization technique of PA6-6X copolymer provided by the invention and the step process of PA6-6X copolymer
Figure.
Specific embodiment
The present invention in order to solve the problems existing in the prior art, provide a kind of PA6-6X copolymer continuous polymerization technique and
PA6-6X copolymer, monomeric unit has better random distribution in the copolymer, shows lower fusing point, thus more suitable
In practical.
It is of the invention to reach the technical means and efficacy that predetermined goal of the invention is taken further to illustrate, below in conjunction with
Attached drawing and preferred embodiment, to the continuous polymerization technique and PA6-6X copolymer of PA6-6X copolymer proposed according to the present invention,
The effect of its specific embodiment, structure, feature, detailed description is as follows.In the following description, different " embodiment " or
What " embodiment " referred to is not necessarily the same embodiment.In addition, the special characteristic, structure or feature in one or more embodiments can
It is combined by any suitable form.
The terms "and/or", only a kind of incidence relation for describing affiliated partner, indicates that there may be three kinds of passes
System, it is specific to understand for example, A and/or B are as follows: it can simultaneously include A and B, can be with individualism A, it can also be with individualism
B can have above-mentioned three kinds of any case.
In signified PA6-6X copolymer of the invention, nylon 6X salt can be nylon 612 salt or nylon 610 salt.
1 embodiment 1-18 is the example of PA6-612
1) embodiment 1-6 is not for adding concentrate
Embodiment 1
A. the fresh molten caprolactam of 570kg and 612 salt of 12kg solid nylon are added in mixed flow container per hour,
Under the conditions of 100 DEG C, by stirring 10min, mixture I is obtained.
B. by mixture I, 27.3kg nylon 612 saline solution (concentration wt.66%) and 1.8kg terephthalic acid (TPA)
(PTA) it is mixed in static mixer, polymerize to form prepolymer subsequently into first reactor, the pressure of first reactor is
10bar, temperature are 265 DEG C, residence time 3h, and the conversion ratio of nylon 612 salt is 97%.
C. first reactor prepolymer is sent to the first amide exchanger, the first amide exchanger temperature is 266 DEG C, is stopped
Time is 1.5h, and pressure drops to 5bar from 10bar.
D. the first amide exchanger material is sent to second reactor, second reactor temperature is 265 DEG C, and reaction pressure is
5bar, residence time 3h.
E. second reactor material is sent by the second amide exchanger to third reactor, the temperature of third reactor is
255 DEG C, reaction pressure 20mbar, residence time 12h.And by 0.6m3The nitrogen of/ton slice leads to third reactor top
Moisture content is separated in material.After reaction, obtain copolymer, then copolymer through supercooling, pelletizing, extract and be dried to obtain
It is copolymerized PA6-612, relative viscosity 2.6, fusing point is 208.1 DEG C.
Embodiment 2-6 is the example of caprolactam and nylon 612 salt different proportion and different output, use and embodiment
1 similar preparation process, polymerization process condition and product index see the table below.
2) embodiment 7-10 is for adding concentrate
Embodiment 7
A. the fresh molten caprolactam of 532.8kg and 612 salt of 1.2kg solid nylon are added in mixed flow container per hour,
Under the conditions of 190 DEG C, 0.5min is dispersed by shearing, obtains mixture I.
B. mixture I, 95.7kg concentrate (concentration wt.69%), 0.12kgPTA are mixed in static mixer,
It polymerize to form prepolymer subsequently into first reactor, the pressure of first reactor is 8bar, and temperature is 245 DEG C, the residence time
For 1h, the conversion ratio of nylon 612 salt is 98%.
C. first reactor prepolymer is sent to the first amide exchanger, the first amide exchanger temperature is 245 DEG C, is stopped
Time is 0.5h, and pressure drops to 3bar from 8bar.
D. the first amide exchanger material is sent to second reactor, second reactor temperature is 255 DEG C, and reaction pressure is
3bar, residence time 3h.
E. second reactor material is sent by the second amide exchanger to third reactor, the temperature of third reactor is
250 DEG C, reaction pressure 50mbar, residence time 10h.And by 0.1m3The nitrogen of/ton slice leads to third reactor top
Moisture content is separated in material.After reaction, copolymer is obtained, wherein extractable is 7.5wt.%, and cyclic oligomer contains
Amount be 0.15wt.%, cyclic dimer content 0.075wt.%, copolymer through supercooling, pelletizing, extract and be dried to obtain
It is copolymerized PA6-612.Copolymer relative viscosity is 3.0, and fusing point is 218.8 DEG C.
Embodiment 8-10 uses preparation process similar to Example 7, and polymerization process condition and product index see the table below.
3) embodiment 11-18 is for adding catalyst
In this group of embodiment, catalyst is one kind of auxiliary agent, in addition to this it is possible to common in nylon polymerization reaction
Additive as auxiliary agent.
Embodiment 12
A. the fresh molten caprolactam of 480kg and 612 salt of 90kg solid nylon are added in mixed flow container per hour,
Under the conditions of 100 DEG C, by mixed allocation 40min, mixture I is obtained.
B. by mixture I, 45.5kg nylon 612 saline solution (concentration wt.66%), 1.8kgPTA, 0.3kg zinc acetate
It being mixed in static mixer, polymerize to form prepolymer subsequently into first reactor, the pressure of first reactor is 20bar,
Temperature is 265 DEG C, residence time 3h, and the conversion ratio of nylon 612 salt is 95%.
C. first reactor prepolymer is sent to the first amide exchanger, the first amide exchanger temperature is 266 DEG C, is stopped
Time is 1.5h, and pressure drops to 5bar from 20bar.
D. the first amide exchanger material is sent to second reactor, second reactor temperature is 265 DEG C, and reaction pressure is
5bar, residence time 3h.
E. second reactor material is sent by the second amide exchanger to third reactor, the temperature of third reactor is
255 DEG C, reaction pressure 20mbar, residence time 12h.And by 0.6m3The nitrogen of/ton slice leads to third reactor top
Moisture content is separated in material.After reaction, copolymer is obtained.Copolymer through supercooling, pelletizing, extract and be dried to obtain copolymerization
PA6-612.Copolymer relative viscosity is 2.6, and fusing point is 184.2 DEG C.
Embodiment 11 uses preparation process identical with embodiment 12, and embodiment 13-18 is using similar to Example 12
Preparation process, polymerization process condition and product index see the table below.
Since caprolactam is different from the reactivity of PA612 salt, reaction rate, product structure and properties of product are caused
Difference promotes the amide exchange reaction of Nylon 6 Chains section and nylon 612 segment to obtain by adding the catalyst of amide exchange reaction
To the PA6-612 product of high degree of randomness, comparative example 11 and 12, embodiment 13 and 14, embodiment 15 and 16, embodiment 17 with
18, using identical polymerization technique, the PA6-612 product ratio for adding catalyst is not added with catalyst with lower fusing point.
2 embodiments 19 are the example of PA6-610
Embodiment 19
A. the fresh molten caprolactam of 378kg and 610 salt of 180kg solid nylon are added in mixed flow container per hour,
Under the conditions of 100 DEG C, by grinding 60min, mixture I is obtained.
B. by mixture I, 63.6kg nylon 610 saline solution (concentration wt.66%), 1.8kgPTA in static mixer
Interior mixing polymerize to form prepolymer subsequently into first reactor, and the pressure of first reactor is 20bar, and temperature is 265 DEG C,
Residence time is 3h, and the conversion ratio of nylon 610 salt is 92%.
C. first reactor prepolymer is sent to the first amide exchanger, the first amide exchanger temperature is 266 DEG C, is stopped
Time is 1.5h, and pressure drops to 5bar from 20bar.
D. the first amide exchanger material is sent to second reactor, second reactor temperature is 265 DEG C, and reaction pressure is
5bar, residence time 3h.
E. second reactor material is sent by the second amide exchanger to third reactor, the temperature of third reactor is
255 DEG C, reaction pressure 20mbar, residence time 12h.And by 0.6m3The nitrogen of/ton slice leads to third reactor top
Moisture content is separated in material.After reaction, obtain copolymer, then copolymer through supercooling, pelletizing, extract and be dried to obtain
It is copolymerized PA6-610, relative viscosity 2.6, fusing point is 169.6 DEG C.
Although preferred embodiments of the present invention have been described, it is created once a person skilled in the art knows basic
Property concept, then additional changes and modifications may be made to these embodiments.So it includes excellent that the following claims are intended to be interpreted as
It selects embodiment and falls into all change and modification of the scope of the invention.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.If in this way, these modifications and changes of the present invention belong to the equivalent technologies of the claims in the present invention range it
Interior, then the present invention is also intended to include these modifications and variations.
Claims (19)
1. a kind of continuous polymerization technique of PA6-6X copolymer, which is characterized in that polymerize using three-stage, use caprolactam
(CPL) it mixes subsequently into high-temperature high-voltage reaction device produce PA6-6X copolymer before the reaction with nylon 6X salt, including with
Lower step:
1) it is mixed to get mixture I in mixed flow container using caprolactam and solid nylon 6X salt, by mixture I, nylon 6X salt
Aqueous solution mixes in pipe-line mixer；
2) material that step 1) mixes is sent to first reactor to polymerize to form prepolymer；
3) material after first reactor is sent to the first amide exchanger, and the material after the first amide exchanger is sent to the second reaction
Device；
4) material for obtaining step 3) is sent to the second amide exchanger, and the material after the second amide exchanger, which is sent to third, to react
Device；
5) the PA6-6X Copolymer Melts for obtaining step 4) carry out pelletizing by pelleter, then using extraction, it is dry after
Obtain PA6-6X copolymer slice finished product；
The catalyst of step 1) the addition amide exchange reaction；
The catalyst is shown in Formulas I
R1-SO3-R2 I
Wherein R1Represent the alkyl group containing 1 to 16 carbon atom or phenyl or aminomethyl phenyl；R2Represent Li, Na or K；
And/or the catalyst is one or more of zinc acetate, magnesium acetate, stannous octoate.
2. the continuous polymerization technique of PA6-6X copolymer according to claim 1, which is characterized in that the caprolactam is
The mixture of fresh caprolactam or fresh caprolactam and the caprolactam by recycling.
3. the continuous polymerization technique of PA6-6X copolymer according to claim 2, which is characterized in that the fresh acyl in oneself
The mass content of fresh caprolactam is not less than 50% in the mixture of amine and the caprolactam by recycling.
4. the continuous polymerization technique of PA6-6X copolymer according to claim 1, which is characterized in that the nylon 6X salt is
Nylon 612 salt or nylon 610 salt.
5. the continuous polymerization technique of PA6-6X copolymer according to claim 1, which is characterized in that the solid nylon 6X
The amount of salt is calculated as 0.2-30% based on the total amount of monomer.
6. the continuous polymerization technique of PA6-6X copolymer according to claim 1, which is characterized in that the nylon 6X salt water
Concentration of polymer solution is in 62%-80%.
7. the continuous polymerization technique of PA6-6X copolymer according to claim 6, which is characterized in that the nylon 6X salt water
Concentration of polymer solution is in 62%-75%.
8. the continuous polymerization technique of PA6-6X copolymer according to claim 6, which is characterized in that the nylon 6X salt water
The amount of 6X salt is calculated as 0-30% based on the total amount of monomer in solution.
9. the continuous polymerization technique of PA6-6X copolymer according to claim 1, which is characterized in that the first reactor
Pressure 8-50bar, 245-285 DEG C of temperature, residence time 1-4h.
10. the continuous polymerization technique of PA6-6X copolymer according to claim 9, which is characterized in that first reaction
Device pressure 15-38bar, 260-280 DEG C of temperature, residence time 2-3h.
11. the continuous polymerization technique of PA6-6X copolymer according to claim 1, which is characterized in that the catalyst is
One of paratoluenesulfonic acid sodium salt, p-methyl benzenesulfonic acid potassium, dodecyl sodium sulfate, zinc acetate, magnesium acetate, stannous octoate are several
Kind.
12. the continuous polymerization technique of PA6-6X copolymer according to claim 1, which is characterized in that in first reactor
The conversion ratio of interior nylon 6X salt is in 90-98%.
13. the continuous polymerization technique of PA6-6X copolymer according to claim 1, which is characterized in that include three non-pipes
The reactor of road formula, and the amide between first and second and second and third reactor using draw ratio greater than 10,000 exchanges
Device is to strengthen amide exchange reaction.
14. the continuous polymerization technique of PA6-6X copolymer according to claim 13, which is characterized in that first amide
For the control of exchanger temperature at 245-285 DEG C, residence time of the material in the first amide exchanger is 0.5-2h, and pressure is from 8-
50bar is down to 3-6bar.
15. the continuous polymerization technique of PA6-6X copolymer according to claim 13, which is characterized in that second reaction
For the control of device temperature at 255-275 DEG C, pressure control is 2-3h in 3-6bar, the residence time of material.
16. the continuous polymerization technique of PA6-6X copolymer according to claim 13, which is characterized in that the third reaction
The control of device temperature is at 240-255 DEG C, and pressure control is in -50mbar~50mbar, and the residence time of material is 10-12h, by nitrogen
It leads in the material on third reactor top, the consumption of the nitrogen is 0.1-1.5Nm3/ ton slice.
17. the continuous polymerization technique of PA6-6X copolymer according to claim 13, which is characterized in that at second and third
Two reactor heads of reactor use knockout tower or other kinds of technique to separate moisture in the reactor head simultaneously.
18. according to claim 1 in -17 any PA6-6X copolymer continuous polymerization technique, which is characterized in that it is described
PA6-6X copolymer product fusing point between 158.5 DEG C -218.8 DEG C, relative viscosity is between 2.4-3.6.
19. using PA6-6X copolymer made from the continuous polymerization technique any in claim 1~18, feature exists
In,
The value range of the relative viscosity of the PA6-6X copolymer is 2.4-3.6；
The value range of the fusing point of the PA6-6X copolymer is 158.5 DEG C -218.8 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653591A (en) * | 2012-05-23 | 2012-09-05 | 浙江华建尼龙有限公司 | Process for producing caprolactam and nylon 66 salt copolymer slice |
| CN105504267A (en) * | 2016-02-23 | 2016-04-20 | 江苏弘盛新材料股份有限公司 | Three-phase hydrolytic polymerization process for nylon 6 |
| CN105885037A (en) * | 2015-05-12 | 2016-08-24 | 上海凯赛生物技术研发中心有限公司 | Production equipment and method of polyamide 5X |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653591A (en) * | 2012-05-23 | 2012-09-05 | 浙江华建尼龙有限公司 | Process for producing caprolactam and nylon 66 salt copolymer slice |
| CN105885037A (en) * | 2015-05-12 | 2016-08-24 | 上海凯赛生物技术研发中心有限公司 | Production equipment and method of polyamide 5X |
| CN105504267A (en) * | 2016-02-23 | 2016-04-20 | 江苏弘盛新材料股份有限公司 | Three-phase hydrolytic polymerization process for nylon 6 |
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Address after: No. 3, Yan Jing Li Zhongjie, Chaoyang District, Beijing, Beijing Patentee after: China Textile Science Research Institute Co., Ltd. Address before: No. 3, Yan Jing Li Zhongjie, Chaoyang District, Beijing, Beijing Patentee before: Chinese Textile Scientific Research Inst. |
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