CN105131279B - A kind of method that reaction extrusion in-situ polymerization prepares SEBS g PA6 - Google Patents
A kind of method that reaction extrusion in-situ polymerization prepares SEBS g PA6 Download PDFInfo
- Publication number
- CN105131279B CN105131279B CN201510349484.5A CN201510349484A CN105131279B CN 105131279 B CN105131279 B CN 105131279B CN 201510349484 A CN201510349484 A CN 201510349484A CN 105131279 B CN105131279 B CN 105131279B
- Authority
- CN
- China
- Prior art keywords
- sebs
- extruder
- situ polymerization
- reaction extrusion
- prepares
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Polyamides (AREA)
Abstract
The method that a kind of reaction extrusion in-situ polymerization of disclosure of the invention prepares SEBS g PA6, its preparation method includes three below step：(1) pretreatment of the reactive monomer of nylon 6 (caprolactam)；(2) reaction extrusion in-situ polymerization prepares SEBS g PA6；(3) three processes of the purifying of SEBS g PA6.Compared with the existing technology for preparing polymer graft modification SEBS, not only grafting efficiency is high for reaction extrusion in-situ polymerization of the present invention, and also avoid the use of a large amount of organic solvents, it is easy to accomplish the regulation and control of PA6 side chain weight contents in SEBS g PA6, process is simple, can continuously produce.
Description
Technical field
The invention discloses grafting modification polymer arts, more particularly to one kind is with extruder as reactor, passes through
Reaction extrusion in-situ polymerization prepares styrene ethylene butadiene-i.e. SEBS-g-PA6's of styrene block copolymer grafting nylon
Method.
Background technology
Styrene ethylene butadiene-styrene block copolymer (SEBS) is thermoplastic block copolymers styrene-fourth
Prepared by rubber segments polybutadiene unsaturated double-bond is by selection hydrogenation in styrene block copolymer (SBS) molecule
Novel elastomer, the phase region that polystyrene block is formed is scattered in the elastic matrix phase of ethylene-butene copolymer, and by elasticity
Body block interlocking is into physical cross-linked network.It is this with elastomer as continuous phase, polystyrene for dispersed phase network structure assign
The double properties of SEBS plastics and rubber.SEBS have excellent resistance to ozone, resistance to oxidation, UV resistant, electric insulating quality and
Outdoor weather resistance, has preferable wearability and pliability, the SEBS also chemicals such as inorganic acid resistance, alcohols in use.By
It has been always the most commonly used bullet of purposes generally acknowledged in the world since formally being industrialized from the beginning of the eighties in the excellent properties of SEBS
Elastomer material.But, SEBS is seldom used alone, typically all can be with other materials, such as thermoplastic, resin, filler, auxiliary agent
Required performance is obtained etc. being compounded, however, due to not polar functionalities or reactive group on the strand of SEBS,
And the styrene block contained by it is poor with the compatibility of highly polar polymer, this allows for it and polyurethane, polyamide, polyphenyl
The compatibility of the engineering plastics with polarity such as ether, polyester is poor, the dispersion effect that simple melting mixing cannot be stablized.For
Increase the comixing compatibility with polymer, reduce interfacial tension, it is often necessary to which graft modification is carried out to SEBS.
The SEBS (SEBS-g-MA) of modified by maleic acid anhydride graft is typically used as the bulking agent of SEBS toughened polyamide materials,
Its Compatibilization Mechanism is that the maleic anhydride functional groups of SEBS-g-MA react with the Amino End Group of polyamide in Blending Processes, generation
SEBS-g-PA, so as to play compatibilization.However, the reaction between SEBS-g-MA and the Amino End Group of polyamide only occurs in two
Between the interface of person, and the maleic anhydride functional groups ratio that can participate in reacting is not high, therefore, the increase-volume limited efficacy of SEBS-g-MA.
Therefore, if directly using SEBS-g-PA6 as the bulking agent of SEBS toughened polyamide materials, material will more efficiently be improved
Interface compatibility inside material.Currently, successfully included using the case of polymer graft modification SEBS, polymethyl methacrylate
(Chinese invention patent CN201010100150), polyacrylonitrile (Chinese invention patent CN201010100150), PLA (China
Patent of invention CN200710172167) and polyvinylpyrrolidone (Chinese invention patent CN200710038050) etc..Above-mentioned material
Material generally carries out graft reaction using solwution method and fusion method, and solwution method is that polymer is dissolved in into aliphatic hydrocarbon, aromatic hydrocarbon, halo
Graft modification is carried out in hydrocarbon equal solvent, is low system viscosity the characteristics of the technique, mass transfer, heat transfer are easy, are conducive to control anti-
Should, the functionalization degree of polymer is high；But many post processing works such as reacted separation, solvent removal, washing, drying, granulation
Sequence so that trivial operations, cost increases.Fusion-grafting rule is to add SEBS, graft polymers and radical initiator together
Enter in extruder, reacted by the free radical grafting during melt blending, the modified of SEBS is completed, due to not using or only making
A small amount of solvent is used, postprocessing working procedures are relatively easy, advantageously reduce pollution and reduces cost, but, even if strong in the technique
Under immixture, the interfacial reaction volume between two kinds of incompatible polymers is also limited；On the other hand, due to steric effect
Influence, two reactivities of the functional group that reacts to each other relative to much smaller between small molecule functional group, therefore, it is difficult to high
Efficiency system is for pure graft copolymer.
SEBS-g-MA has been the product of scale of mass production, and famous manufacturer includes shell, Asahi Chemical Industry and Li Changrongization
Gong Deng companies.Chinese patent (publication number CN101469071) points out, maleic anhydride functional groups can as cyclic lactames it is cloudy from
The initiator of sub- ring-opening polymerisation, the method that the patent passes through anionic polymerisation realizes the preparation of polyamide grafts copolymer.Base
Demand, the research and development present situation of present polymer graft modification SEBS and SEBS-g-MA in SEBS toughened polyamide materials
The characteristics of, this patent proposes a kind of method that reaction extrusion in-situ polymerization prepares SEBS-g-PA6, the method letter described in the invention
It is single, effective, it is easy to accomplish the serialization industrial production of SEBS-g-PA6.
The content of the invention
Goal of the invention：In order to overcome the deficiencies in the prior art, the present invention to provide a kind of simple, effective and be easy to real
The industrial method for preparing SEBS-g-PA6 of existing serialization.
Technical scheme：In order to solve the above technical problems, a kind of reaction extrusion in-situ polymerization that the present invention is provided prepares SEBS-
The method of g-PA6, comprises the following steps that：
(1) pretreatment of reactive caprolactam：Heating, molten caprolactam simultaneously remove wherein micro moisture, treatment
Caprolactam afterwards is stored in isolation air, and the constant liquid addition tank of temperature, is subsequently adding caprolactam anion and is gathered
The catalyst of conjunction, is well mixed, standby；
(2) reaction extrusion in-situ polymerization：Extruder is opened, the SEBS-g-MA by dried process is extruded by feeding machine
The charging aperture of machine adds extruder；Using measuring pump, above the extruded machine machine barrel of blend melt obtained in step (1)
Exhaust outlet adds extruder, and SEBS-g-PA6 is prepared eventually through reactive extrursion.
(3) purify：Unreacted acyl in oneself in resulting SEBS-g-PA6 crude products in step (2) is washed away using boiling water
Amine monomers, remove after the product after monomer is dried and both obtain SEBS-g-PA6.
Further, in step (1), the temperature of caprolactam melt water removal is 80~180 DEG C, and caprolactam anion gathers
The catalyst of conjunction is selected from alkali metal, the hydride of alkali metal, the hydroxide or alcoholates of alkali metal, and catalyst charge is for oneself
0.1~2wt% of lactam monomers, the storage temperature of reactive melt is 80~180 DEG C, and isolation air ambient is nitrogen, hydrogen
A kind of gaseous environment in gas, argon gas and helium.
Further, the SEBS-g-MA in step (2), its grafting rate is 1.0~1.5wt%.
Further, the extruder in step (2) is double screw extruder, and the exhaust outlet on machine barrel compresses positioned at extruder
Section or metering section, extruder temperature are 50~240 DEG C, and rotating speed is 100~300rpm；A diameter of 20~the 80mm of extruder screw,
Draw ratio is 24~60.
Further, the feed rate ratio of the reactive monomer in step (2) obtained in SEBS-g-MA and step (1)
It is 1：0.05~10.
Beneficial effect：The present invention in terms of existing technologies, possesses advantages below：
Not only grafting efficiency is high for the method that the present invention is provided, but also can avoid the use of a large amount of organic solvents, is easy to again
The regulation and control of PA6 side chain grafting rates are realized, the compatibility that can preferably solve in SEBS toughened polyamide material Blending Processes is asked
Topic.The method process is simple, can continuously produce.
Specific embodiment
The present invention is further described below in conjunction with the accompanying drawings.
Embodiment 1
Weigh in 0.5Kg caprolactams addition there-necked flask, be heated to 180 DEG C of meltings, it is micro- in vacuum distillation removing system
The water of amount, nitrogen charging gas shielded adds the sodium for accounting for caprolactam gross weight 0.1wt%, after stirring and dissolving, by molten mass storage
In 180 DEG C of thermostatic tank；It is another to weigh the SEBS-g-MA that 10Kg grafting rates are 1.5wt%, in the hopper of addition extruder.Open
Open the double screw extruder by preheating, extruder screw diameter 20mm, draw ratio 40, the setting of reactive extrursion condition：Plus
Material mouth to the temperature of metering section is increased to 240 DEG C successively by 50 DEG C, and head temperature is：220 DEG C, by extruder screw speed setting
It is 100rpm.SEBS-g-MA in hopper adds extruder, the reactivity in isothermal liquid storage tank by feeding machine through charge door
Monomer is added via the steam vent positioned at extruder barrel compression section, and SEBS-g-MA is with the feed rate ratio of reactive monomer
1：0.05.After the material of reaction extrusion in-situ polymerization is through tie rod, granulation, boiled in 90 DEG C of water 12 hours, removing is therein not
Polymerized monomer；Water boil after sample drying after, washed with formic acid, remove wherein non-grafted PA6, then wash, dry, obtain final product
SEBS-g-PA6 materials.
Embodiment 2
Weigh in 10Kg caprolactams addition there-necked flask, be heated to 80 DEG C of meltings, it is micro in vacuum distillation removing system
Water, nitrogen charging gas shielded adds the caustic alcohol for accounting for caprolactam gross weight 2wt%, after stirring and dissolving, by the molten mass storage
In 80 DEG C of thermostatic tank；It is another to weigh the SEBS-g-MA that 1Kg grafting rates are 1.0wt%, in the hopper of addition extruder.Open
By the double screw extruder for preheating, extruder screw diameter 20mm, draw ratio 40, the setting of reactive extrursion condition：Charging
Mouth to the temperature of metering section is increased to 240 DEG C successively by 50 DEG C, and head temperature is：220 DEG C, by extruder screw speed setting
It is 300rpm.SEBS-g-MA in hopper adds extruder, the reactivity in isothermal liquid storage tank by feeding machine through charge door
Monomer is added via the steam vent positioned at extruder barrel metering section, and SEBS-g-MA is with the feed rate ratio of reactive monomer
1：10.After the material of reaction extrusion in-situ polymerization is through tie rod, granulation, boiled in 90 DEG C of water 12 hours, remove therein not gathering
Close monomer；Water boil after sample drying after, washed with formic acid, remove wherein non-grafted PA6, then wash, dry, obtain final product
SEBS-g-PA6 materials.
Embodiment 3
Weigh in 5Kg caprolactams addition there-necked flask, be heated to 80 DEG C of meltings, it is micro in vacuum distillation removing system
Water, nitrogen charging gas shielded adds the caustic alcohol for accounting for caprolactam gross weight 1%, after stirring and dissolving, the molten mass is stored in
In 130 DEG C of thermostatic tank；It is another to weigh the SEBS-g-MA that 1Kg grafting rates are 1.1wt%, in the hopper of addition extruder.Open warp
Cross the double screw extruder of preheating, extruder screw diameter 40mm, draw ratio 60, the setting of reactive extrursion condition：Charge door
Temperature to metering section is increased to 240 DEG C successively by 50 DEG C, and head temperature is：220 DEG C, it is by extruder screw speed setting
200rpm.SEBS-g-MA in hopper adds extruder by feeding machine through charge door, and the reactivity in isothermal liquid storage tank is single
Body is added via the steam vent positioned at extruder barrel metering section, and SEBS-g-MA is 1 with the feed rate ratio of reactive monomer：
5.After the material of reaction extrusion in-situ polymerization is through tie rod, granulation, boiled in 90 DEG C of water 12 hours, remove unpolymerized list therein
Body；Water boil after sample drying after, washed with formic acid, remove wherein non-grafted PA6, then wash, dry, obtain final product SEBS-g-
PA6 materials.
Embodiment 4
Weigh in 1Kg caprolactams addition there-necked flask, be heated to 140 DEG C of meltings, it is micro in vacuum distillation removing system
Water, nitrogen charging gas shielded adds the NaOH for accounting for caprolactam gross weight 0.5%, after stirring and dissolving, by the molten mass storage
It is stored in 140 DEG C of thermostatic tank；It is another to weigh the SEBS-g-MA that 20Kg grafting rates are 1.2wt%, in the hopper of addition extruder.
Open the double screw extruder by preheating, extruder screw diameter 80mm, draw ratio 40, the setting of reactive extrursion condition：
Charge door to the temperature of metering section is increased to 240 DEG C successively by 50 DEG C, and head temperature is：220 DEG C, extruder screw rotating speed is set
It is set to 200rpm.SEBS-g-MA in hopper adds extruder, the reaction in isothermal liquid storage tank by feeding machine through charge door
Property monomer added via the steam vent positioned at extruder barrel metering section, the feed rate ratio of SEBS-g-MA and reactive monomer
It is 1：0.05.After the material of reaction extrusion in-situ polymerization is through tie rod, granulation, boiled in 90 DEG C of water 12 hours, removed therein
Unconverted monomer；Water boil after sample drying after, washed with formic acid, remove wherein non-grafted PA6, then wash, dry, obtain final product
SEBS-g-PA6 materials.
Embodiment 5
Weigh in 1Kg caprolactams addition there-necked flask, be heated to 140 DEG C of meltings, it is micro in vacuum distillation removing system
Water, nitrogen charging gas shielded adds the NaOH for accounting for caprolactam gross weight 0.5%, after stirring and dissolving, by the molten mass
It is stored in 140 DEG C of thermostatic tank；It is another to weigh the SEBS-g-MA that 20Kg grafting rates are 1.2wt%, add the hopper of extruder
In.The double screw extruder by preheating is opened, extruder screw diameter 30mm, draw ratio 60, reactive extrursion condition sets
It is fixed：Charge door to the temperature of metering section is increased to 240 DEG C successively by 50 DEG C, and head temperature is：220 DEG C, extruder screw is turned
Speed is set as 200rpm.SEBS-g-MA in hopper adds extruder by feeding machine through charge door, in isothermal liquid storage tank
Reactive monomer is added via the steam vent positioned at extruder barrel compression section, and SEBS-g-MA is fast with the charging of reactive monomer
Rate ratio is 1：0.05.After the material of reaction extrusion in-situ polymerization is through tie rod, granulation, boiled in 90 DEG C of water 12 hours, remove it
In unconverted monomer；Water boil after sample drying after, washed with formic acid, remove wherein non-grafted PA6, then wash, dry,
Obtain final product SEBS-g-PA6 materials.
Sample prepared in the various embodiments described above, according to document (Cai-Liang Zhanga, Lian-Fang
Feng, Xueping Gua, Sandrine Hoppe, Guo-Hua Hu, Determination of the molar mass of
polyamide block/graft copolymers by size-exclusion chromatography at room
Temperature, Polymer Testing, 2007,26,793-802) in method of testing, determine the content of grafted chain PA6,
Test result is as shown in table 1.
Table 1：The weight content of PA6 side chains in SEBS-g-PA6 prepared by each embodiment
The performance test of embodiment 1：
20 parts, 100 parts PA6 of SEBS-g-PA6 materials prepared in Example 1, are tentatively well mixed through high mixer,
Melt blending in double screw extruder is added, extrusion, granulation obtain the PA6 alloys of SEBS toughness reinforcings, the mechanical property of the alloy
It is shown in Table 2.
The performance test of embodiment 2：
20 parts, 100 parts PA6 of SEBS-g-PA6 materials prepared in Example 2, are tentatively well mixed through high mixer,
Melt blending in double screw extruder is added, extrusion, granulation obtain the PA6 alloys of SEBS toughness reinforcings, the mechanical property of the alloy
It is shown in Table 2.
The performance test of embodiment 3
20 parts, 100 parts PA6 of SEBS-g-PA6 materials prepared in Example 3, are tentatively well mixed through high mixer,
Melt blending in double screw extruder is added, extrusion, granulation obtain the PA6 alloys of SEBS toughness reinforcings, the mechanical property of the alloy
It is shown in Table 2.
The performance test of embodiment 4
20 parts, 100 parts PA6 of SEBS-g-PA6 materials prepared in Example 4, are tentatively well mixed through high mixer,
Melt blending in double screw extruder is added, extrusion, granulation obtain the PA6 alloys of SEBS toughness reinforcings, the mechanical property of the alloy
It is shown in Table 2.
The performance test of embodiment 5
20 parts, 100 parts PA6 of SEBS-g-PA6 materials prepared in Example 5, are tentatively well mixed through high mixer,
Melt blending in double screw extruder is added, extrusion, granulation obtain the PA6 alloys of SEBS toughness reinforcings, the mechanical property of the alloy
It is shown in Table 2.
Comparative example 6
20 parts, 100 parts PA6 of commercialization SEBS-g-MA materials that grafting rate is 2% are taken, are tentatively well mixed through high mixer,
Melt blending in double screw extruder is added, extrusion, granulation obtain the PA6 alloys of SEBS toughness reinforcings, the mechanical property of the alloy
It is shown in Table 2.
Table 2：Properties of product test table
| Tensile strength/MPa | Elongation at break/% | Notch impact strength/KJ/m2 | |
| Embodiment 1 | 51 | 185 | 77 |
| Embodiment 2 | 53 | 183 | 76 |
| Embodiment 3 | 50 | 183 | 73 |
| Embodiment 4 | 51 | 180 | 75 |
| Embodiment 5 | 55 | 178 | 73 |
| Comparative example 6 | 42 | 175 | 62 |
The SEBS-g-PA6 prepared by the inventive method is can be seen that from embodiments of the invention and comparative example, its PA6 branch
The grafting rate of chain is higher, because the PA6 side chains that molecule has in itself are fully compatible with PA6, in the material of toughness reinforcing PA6, and SEBS-
G-PA6 has more preferable compatibility than SEBS-g-MA, therefore, in the case of addition identical, SEBS-g-PA6 of the present invention exists
To there is smaller dispersed phase size in PA6 matrixes, there is more obviously raising to its notch impact strength.Additionally, in addition
In the case of identical, the rubber-phase content of low modulus is few compared with SEBS-g-MA in SEBS-g-PA6 of the present invention, to the strong of toughness reinforcing alloy
Degree loss is weak compared with SEBS-g-MA, therefore, compared with SEBS-g-MA, SEBS-g-PA6 of the present invention has compared with the PA6 alloys of toughness reinforcing
Tensile strength higher.
Embodiment described above 1-5 is only the preferred embodiment of the present invention, it should be pointed out that：It is general for the art
For logical technical staff, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improve and
Retouching also should be regarded as protection scope of the present invention.
Claims (6)
1. a kind of method that reaction extrusion in-situ polymerization prepares SEBS-g-PA6, it is characterised in that the method is comprised the following steps：
(1) pretreatment of reactive caprolactam monomer：Monomer caprolactam is heated and is melted, depressurized at 80~180 DEG C and steamed
Evaporate, remove wherein moisture, the caprolactam melt after treatment is stored in the liquid addition tank of isolation air, 80~180 DEG C of constant temperature
In, add the catalyst of caprolactam anionic polymerisation and be well mixed；
(2) reaction extrusion in-situ polymerization：Open extruder, by feeding machine, will by dried process, be stored in extruder hopper
Modified by maleic acid anhydride graft the extruded machines of SEBS charging aperture add extruder；Using measuring pump, will be obtained in step (1)
The exhaust outlet above the extruded machine machine barrel of blend melt for obtaining adds extruder, is polymerized eventually through reaction extrusion in-situ and prepares
SEBS-g-PA6, wherein, the extruder in described step (2) is double screw extruder, and the exhaust outlet on machine barrel is located at extrusion
Machine compression section or metering section, the SEBS of modified by maleic acid anhydride graft and the mixing obtained in step (1) in described step (2)
Melt, both feed rate ratios are 1: 0.1~10；
(3) purify：Unreacted caprolactam list in resulting SEBS-g-PA6 crude products in step (2) is washed away using boiling water
Body, removes after the product after monomer is dried and obtains final product SEBS-g-PA6.
2. the method that a kind of reaction extrusion in-situ polymerization according to claim 1 prepares SEBS-g-PA6, it is characterised in that：
The catalyst of caprolactam anionic polymerisation is selected from alkali metal, the hydride of alkali metal, the hydrogen of alkali metal in described step (1)
One or more in oxide or alcoholates.
3. the method that a kind of reaction extrusion in-situ polymerization according to claims 1 or 2 prepares SEBS-g-PA6, its feature
It is：Catalyst charge in described step (1) is 0.1~2wt% of caprolactam monomer.
4. the method that a kind of reaction extrusion in-situ polymerization according to claim 1 prepares SEBS-g-PA6, described step
(1) the isolation air ambient in is a kind of gaseous environment in nitrogen, hydrogen, argon gas and helium.
5. the method that a kind of reaction extrusion in-situ polymerization according to claim 1 prepares SEBS-g-PA6, it is characterised in that：
The SEBS raw materials of the modified by maleic acid anhydride graft in described step (2), its grafting rate is 1.0~1.5wt%.
6. the method that a kind of reaction extrusion in-situ polymerization according to claim 1 prepares SEBS-g-PA6, it is characterised in that
It is characterized in that：；Extruder temperature is 80~240 DEG C in described step (2)；Rotating speed is 100~300rpm；Extruder screw
A diameter of 20~80mm, draw ratio is 24~60.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510349484.5A CN105131279B (en) | 2015-06-23 | 2015-06-23 | A kind of method that reaction extrusion in-situ polymerization prepares SEBS g PA6 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510349484.5A CN105131279B (en) | 2015-06-23 | 2015-06-23 | A kind of method that reaction extrusion in-situ polymerization prepares SEBS g PA6 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105131279A CN105131279A (en) | 2015-12-09 |
| CN105131279B true CN105131279B (en) | 2017-06-16 |
Family
ID=54716887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510349484.5A Active CN105131279B (en) | 2015-06-23 | 2015-06-23 | A kind of method that reaction extrusion in-situ polymerization prepares SEBS g PA6 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105131279B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105949759B (en) * | 2016-05-27 | 2018-10-23 | 江苏苏能新材料科技有限公司 | A kind of reactive extrursion preparation method of conductive polymer nanometer composite material |
| CN107474244B (en) * | 2017-08-18 | 2019-05-10 | 浙江心源科技有限公司 | A kind of preparation method of twin-screw reactive extrursion type nylon elastomer |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153064B (en) * | 2006-09-27 | 2010-11-17 | 上海杰事杰新材料股份有限公司 | Method of producing nylon fuel oil by original position common mixing |
| CN101319089B (en) * | 2007-06-07 | 2011-05-04 | 上海杰事杰新材料股份有限公司 | Low-temperature resistant buckle-against toughening nylon alloy and preparation method thereof |
-
2015
- 2015-06-23 CN CN201510349484.5A patent/CN105131279B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105131279A (en) | 2015-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103012794B (en) | Preparation method of polyamide-imide copolymer | |
| KR102041171B1 (en) | Low cis-polybutadiene rubber and composition and aromatic vinyl resin, and preparation method therof | |
| EP3564287B1 (en) | Aramid-based epoxy resin and preparation method thereof | |
| CN105131279B (en) | A kind of method that reaction extrusion in-situ polymerization prepares SEBS g PA6 | |
| CN105601814A (en) | Industrialized production method of trans-butadiene-isoprene copolymer rubber | |
| CN112920415B (en) | Amidated graphene/nylon 6 nanocomposite and preparation method thereof | |
| CN108070140A (en) | Fibre modifier and modified fibre and its preparation method and application and PP composite material and preparation method thereof | |
| CN101469126A (en) | Copolymerization nylon composition and preparation thereof | |
| CN102391642A (en) | Preparation method of modified monomer cast (MC) nylon 6 blending material | |
| CN100473690C (en) | Organic fibre based on an epoxy resin and a rheology-controlling agent and corresponding dry goods | |
| CN109796730A (en) | Liquid-crystal polyester resin compound with shock resistance and preparation method thereof | |
| CN105622850A (en) | Efficient and environment-friendly preparation method of double-monomer solid-phase grafted PP (polypropylene) | |
| CN102558697A (en) | Preparation method of ultrahigh-toughness polystyrene resin | |
| KR20110063947A (en) | A MANUFACTURING METHOD FOR MALEIMIDE-α-ALKYL STYRENE BASED HEAT-RESISTANT TETRA-POLYMER WITH LOW MOLTEN VISCOSITY AND EXCELLENT COMPATIBILITY | |
| CN109504084A (en) | A kind of toughening modifying nylon | |
| CN108948554B (en) | Polyolefin type polyurethane elastomer toughened polystyrene blending material and preparation method thereof | |
| CN103289079B (en) | Composite material of nylon 6/aramid fibres and preparation method for same | |
| CN114045042B (en) | Bamboo-plastic composite material for container bottom plate and preparation method thereof | |
| CN113583163A (en) | Production system for switching production of GPPS (general purpose polystyrene) and HIPS (high impact polystyrene) products | |
| CN102276914A (en) | Method for preparing organic microcrystal white mica/nylon6/polypropylene (PP)composite material | |
| CN113527584A (en) | Switching method for switching GPPS production method to HIPS production method | |
| CN109206713A (en) | A kind of preparation method and application of the Recycled HDPE composite material containing Poplar Powder | |
| CN109161188A (en) | A kind of high-performance glass fiber/graphene nylon 6 composite material preparation method | |
| CN106928542A (en) | A kind of polypropylene/polyphenylene oxide PP/PPO alloys and preparation method thereof | |
| CN113637117B (en) | Switching method for switching HIPS production method to GPPS production method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180312 Address after: No. 93, Shengyuan Road, Dantu District, Zhenjiang, Jiangsu Patentee after: Mstar Technology Ltd, Jiangsu, Jiangsu Address before: 212003 Zhenjiang City, Jiangsu province dream Creek Road, No. 2 Patentee before: Jiangsu University of Science and Technology |