CN113968940A - Method for preparing low-odor polypropylene grafted maleic anhydride beads under assistance of supercritical carbon dioxide - Google Patents
Method for preparing low-odor polypropylene grafted maleic anhydride beads under assistance of supercritical carbon dioxide Download PDFInfo
- Publication number
- CN113968940A CN113968940A CN202111433284.XA CN202111433284A CN113968940A CN 113968940 A CN113968940 A CN 113968940A CN 202111433284 A CN202111433284 A CN 202111433284A CN 113968940 A CN113968940 A CN 113968940A
- Authority
- CN
- China
- Prior art keywords
- maleic anhydride
- parts
- polypropylene
- carbon dioxide
- supercritical carbon
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention provides a method for preparing low-odor polypropylene grafted maleic anhydride beads under the assistance of supercritical carbon dioxide, which comprises the following steps: 100 parts of polypropylene, 0.5-3 parts of maleic anhydride, 0.5-3 parts of monomer, 0.1-1 part of antioxidant and 0.1-1 part of initiator are uniformly mixed in parts by weight, supercritical carbon dioxide is added, the mixture is vacuumized and then is extruded into strips, and then cooling, air cooling, dewatering and granulating are sequentially carried out, so that the low-odor polypropylene grafted maleic anhydride beads are obtained. Compared with the prior art, the method is carried out under the assistance of supercritical carbon dioxide, and the prepared polypropylene grafted maleic anhydride beads have low smell and narrow molecular weight distribution; the maleic anhydride grafting rate is high, and the mechanical property is excellent; the processing temperature is low, the cost is low, and continuous production can be realized; can be applied to the fields of automobiles, household electrical appliances, cables, packaging materials and the like.
Description
Technical Field
The invention belongs to the technical field of polymers, and particularly relates to a method for preparing low-odor polypropylene grafted maleic anhydride beads under the assistance of supercritical carbon dioxide.
Background
Polypropylene is one of five general-purpose plastics, has wide application fields and is one of important commercial polyolefins, but the common polypropylene lacks polar groups, so that the adhesion, the paint capability, the affinity to dyes and the like and the compatibility with other polymers are limited, and further the further application of the polypropylene is limited. Fillers such as glass fibers, flame retardants, minerals and the like for modifying polypropylene have high polarity, and when polypropylene is physically blended with the fillers, a compatilizer needs to be added to improve the compatibility of a two-phase interface, otherwise, sample pieces can be peeled, layered and the like during molding.
The polypropylene grafted maleic anhydride is a widely commercialized product for improving the polarity of polypropylene, the currently industrialized polypropylene grafted maleic anhydride mainly uses peroxide as an initiator, and a monomer is maleic anhydride, so that the main problems exist that the polypropylene grafted maleic anhydride can generate a very pungent smell in the production process, the operation environment is poor, the worker is not beneficial to the physical health of workers, the product is easy to yellow, the grafting rate of the polypropylene grafted maleic anhydride monomer is low, and the effect of improving the compatibility of polypropylene is not ideal.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing low-odor polypropylene grafted maleic anhydride beads with the aid of supercritical carbon dioxide, wherein the beads prepared by the method have low odor and high mechanical properties.
The invention provides a method for preparing low-odor polypropylene grafted maleic anhydride beads under the assistance of supercritical carbon dioxide, which comprises the following steps:
uniformly mixing 100 parts by weight of polypropylene, 0.5-3 parts by weight of maleic anhydride, 0.5-3 parts by weight of monomer, 0.1-1 part by weight of antioxidant and 0.1-1 part by weight of initiator, injecting supercritical carbon dioxide, vacuumizing, extruding and bracing, and sequentially cooling, air-cooling to remove water and granulating to obtain low-odor polypropylene grafted maleic anhydride beads;
the monomer is selected from one or more of styrene, cyclopentadiene and thiuram;
the initiator is selected from one or more of benzoyl peroxide, bis (tert-butylperoxyisopropyl) benzene (BIPB), 2, 3-dimethyl-2, 3-diphenyl butane and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane.
In the invention, the pressure of the supercritical carbon dioxide is 7.38-10.0 MPa, preferably 7.38-9 MPa.
In the present invention, the antioxidant is selected from one or more of hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants.
In the present invention, the polypropylene is selected from isotactic polypropylene;
the melt flow index of the polypropylene is 1-50 g/10 min. The polypropylene is preferably dried before use.
In the invention, the supercritical carbon dioxide is added at 1-5% of the feeding speed of the polypropylene.
In the present invention, the preparation process is carried out in a twin-screw extruder;
the double-screw extruder has 12 sections from the feed opening to the heating zone of the machine head, and the sections are sequentially set to 160-170 ℃, 170-190 ℃, 160-195 ℃, 160-210 ℃, 160-220 ℃ and 160-210 ℃. Preferably, the double-screw extruder has 12 sections from the feed opening to the heating zone of the machine head, and the temperature is set to 165 ℃, 180 ℃, 170-190 ℃, 170-195 ℃, 170-210 ℃ and 170-210 ℃ in sequence. The rotating speed of the screw is 150 r/min-400 r/min, preferably 150-300 r/min; the feeding rotating speed is 10kg/h to 50kg/h, preferably 10kg/h to 30 kg/h. In a specific embodiment, the double-screw extruder has 12 sections from the feed opening to the heating zone of the head, and the sections are sequentially set to 165 ℃, 180 ℃, 185 ℃, 195 ℃ and 195 ℃; the rotation speed of the screw is 200rpm, 300rpm or 250 rpm; the feeding speed is 10kg/h, or 15kg/h or 20 kg/h.
In the invention, the low-odor polypropylene grafted maleic anhydride beads have the length of 1-1.5 mm and the diameter of 0.5-1.5 mm. In a specific example, the low odor polypropylene grafted maleic anhydride beads were 1.5mm in length and 1.2mm in diameter.
In the invention, the low-odor polypropylene grafted maleic anhydride beads (PP-g-MAH) prepared under the assistance of supercritical carbon dioxide are modified polypropylene particles with polarity. The common polypropylene is widely applied to the production of fiber products such as clothes, blankets and the like, medical instruments, automobiles, bicycles, parts, conveying pipelines, chemical containers and the like, and is also used for packaging foods and medicines. However, the lack of polar groups in polypropylene limits its adhesion, paintability, affinity for dyes and printing agents, and compatibility with other polymers. Grafting with maleic anhydride is a widely commercialized method for introducing polarity into polypropylene. At present, domestic polypropylene grafted maleic anhydride products have the problems of high odor, wide relative molecular mass distribution, low grafting rate and the like.
According to the invention, supercritical carbon dioxide is introduced into a melt extrusion process, the supercritical carbon dioxide can play a role of plasticization, the fluidity of a substance in an extruder is improved, the collision between a free radical active site and a maleic anhydride monomer is improved, after the collision probability between the active site and the maleic anhydride monomer is increased, the beta degradation of a polypropylene chain can be obviously reduced, and meanwhile, the grafting rate of the maleic anhydride can be improved; meanwhile, the improvement of the fluidity can reduce the process temperature during processing and reduce the energy consumption; add evacuating device near the aircraft nose position at the screw rod barrel, can utilize carbon dioxide to carry residual monomer, carry out residual monomer more effectively in with the material, reduce the smell nature of final product.
The invention provides a method for preparing low-odor polypropylene grafted maleic anhydride beads under the assistance of supercritical carbon dioxide, which comprises the following steps: 100 parts of polypropylene, 0.5-3 parts of maleic anhydride, 0.5-3 parts of monomer, 0.1-1 part of antioxidant and 0.1-1 part of initiator are uniformly mixed in parts by weight, supercritical carbon dioxide is added, the mixture is vacuumized and then is extruded into strips, and then cooling, air cooling, dewatering and granulating are sequentially carried out, so that the low-odor polypropylene grafted maleic anhydride beads are obtained. Compared with the prior art, the method is carried out under the assistance of supercritical carbon dioxide, and the prepared polypropylene grafted maleic anhydride beads have low smell and narrow molecular weight distribution; the grafting rate of maleic anhydride is high; the processing temperature is low, the cost is low, and continuous production can be realized; the composite material can be applied to the fields of automobiles, household appliances, cables, packaging materials and the like; the mechanical properties are excellent, such as tensile strength, elongation at break, bending strength, bending modulus and impact strength are all higher. The experimental results show that: the odor grade of the polypropylene grafted maleic anhydride bead is 3.0-3.3; the tensile strength is 89.0-90.0 MPa; the elongation at break is 5.9-6.1%; the bending strength is 119.8-120.8 MPa; the flexural modulus is 5828-5853 MPa; the impact strength at normal temperature is 11.9-13.6 KJ/m2。
Detailed Description
To further illustrate the present invention, a method for preparing low-odor polypropylene grafted maleic anhydride beads with the aid of supercritical carbon dioxide, which is provided by the present invention, is described in detail below with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
(1) Drying the polypropylene resin in a plastic mixing dryer for later use; the processing aid is placed in a vacuum drying oven at 60 ℃ for drying for 12h for later use;
(2) weighing various dried raw materials according to a proportion, wherein the weight of the raw materials relative to the polypropylene resin is calculated as 100 parts of polypropylene resin, 10100.1 parts of antioxidant, 1680.1 parts of antioxidant, 1.2 parts of maleic anhydride, 1.2 parts of styrene and 0.1 part of initiator BIPB, placing the weighed raw materials in a high-speed mixer, stirring for 5min, and uniformly mixing the materials;
(3) adding the mixed material into a parallel co-rotating twin-screw extruder, wherein 12 sections are arranged in a heating zone from a feed opening to a machine head, the heating zone is sequentially set to 165 ℃, 180 ℃, 185 ℃, 195 ℃, 200r/min, the feeding rotating speed is 10kg/h, the injection pressure in the screw is 7.5MPa, the vacuumizing operation is carried out at a position close to the machine head, and the low-odor polypropylene grafted maleic anhydride beads with the length of 1.5mm and the diameter of 1.2mm under the assistance of supercritical carbon dioxide are obtained by extrusion, bracing, cooling, air cooling, dewatering and granulating.
Example 2
(1) Drying the polypropylene resin in a plastic mixing dryer for later use; the processing aid is placed in a vacuum drying oven at 60 ℃ for drying for 12h for later use;
(2) weighing various dried raw materials according to a proportion, wherein the weight of the raw materials relative to the polypropylene resin is calculated as 100 parts of polypropylene resin, 10100.1 parts of antioxidant, 1680.1 parts of antioxidant, 1.2 parts of maleic anhydride, 1.0 part of styrene and 0.1 part of initiator BIPB, placing the weighed raw materials in a high-speed mixer, stirring for 5min, and uniformly mixing the materials;
(3) adding the mixed material into a parallel co-rotating twin-screw extruder, wherein 12 sections are arranged in a heating zone from a feed opening to a machine head, the heating zone is sequentially set to 165 ℃, 180 ℃, 185 ℃, 195 ℃, 300r/min, the feeding rotating speed is 20kg/h, the injection pressure in the screw is 7.5MPa, the vacuumizing operation is carried out at a position close to the machine head, and the low-odor polypropylene grafted maleic anhydride beads with the length of 1.5mm and the diameter of 1.2mm under the assistance of supercritical carbon dioxide are obtained through extrusion, bracing, cooling, air cooling, water removal and grain cutting.
Example 3
(1) Drying the polypropylene resin in a plastic mixing dryer for later use; the processing aid is placed in a vacuum drying oven at 60 ℃ for drying for 12h for later use;
(2) weighing various dried raw materials according to a proportion, wherein the weight of the raw materials relative to the polypropylene resin is calculated as 100 parts of polypropylene resin, 10100.1 parts of antioxidant, 1680.1 parts of antioxidant, 1.5 parts of maleic anhydride, 1.3 parts of styrene and 0.15 part of initiator BIPB, placing the weighed raw materials in a high-speed mixer, stirring for 5min, and uniformly mixing the materials;
(3) adding the mixed material into a parallel co-rotating twin-screw extruder, wherein 12 sections are arranged in a heating zone from a feed opening to a machine head, the heating zone is sequentially set to 165 ℃, 180 ℃, 185 ℃, 195 ℃, 250r/min in screw rotation speed, 15kg/h in feeding rotation speed, 7.5MPa in injection pressure in the screw, vacuumizing operation is carried out at a position close to the machine head, and low-odor polypropylene grafted maleic anhydride beads with the length of 1.5mm and the diameter of 1.2mm under the assistance of supercritical carbon dioxide are obtained through extrusion, bracing, cooling, air cooling, water removal and grain cutting.
According to the invention, the granular products prepared in the embodiments 1-3 are respectively added with glass fiber, antioxidant and the like for blending granulation, and the formula is shown in the following table 1:
TABLE 1 formulation composition of test samples of beads prepared in examples and control
The mechanical property test of the test sample prepared in the table 1 is carried out, and the result is shown in the table 2:
TABLE 2 mechanical Property test results of examples and controls
As can be seen from Table 2, the grafted product of the invention does not generate pungent odor in the preparation process, has low odor grade, accords with automobile materials, has excellent mechanical properties, can be applied to the fields of automobiles, household electrical appliances and the like, and is beneficial to reducing the odor problem of environmental pollution in processing.
As can be seen from the above examples, the present invention provides a method for preparing low-odor polypropylene grafted maleic anhydride beads with the aid of supercritical carbon dioxide, comprising the steps of: 100 parts of polypropylene, 0.5-3 parts of maleic anhydride, 0.5-3 parts of monomer, 0.1-1 part of antioxidant and 0.1-1 part of initiator are uniformly mixed in parts by weight, supercritical carbon dioxide is added, the mixture is vacuumized and then is extruded into strips, and then cooling, air cooling, dewatering and granulating are sequentially carried out, so that the low-odor polypropylene grafted maleic anhydride beads are obtained. Compared with the prior art, the method is carried out under the assistance of supercritical carbon dioxide, and the prepared polypropylene grafted maleic anhydride beads have low smell and narrow molecular weight distribution; the maleic anhydride grafting rate is high, and the mechanical property is excellent; the processing temperature is low, the cost is low, and continuous production can be realized; can be applied to the fields of automobiles, household electrical appliances, cables, packaging materials and the like. The experimental results show that: the odor grade of the polypropylene grafted maleic anhydride bead is 3.0-3.3; the tensile strength is 89.0-90.0 MPa; the elongation at break is 5.9-6.1%; the bending strength is 119.8-120.8 MPa; the flexural modulus is 5828-5853 MPa; the impact strength at normal temperature is 11.9-13.6 KJ/m2。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A method for preparing low-odor polypropylene grafted maleic anhydride beads under the assistance of supercritical carbon dioxide, comprising the following steps:
uniformly mixing 100 parts by weight of polypropylene, 0.5-3 parts by weight of maleic anhydride, 0.5-3 parts by weight of monomer, 0.1-1 part by weight of antioxidant and 0.1-1 part by weight of initiator, injecting supercritical carbon dioxide, vacuumizing, extruding and bracing, and sequentially cooling, air-cooling to remove water and granulating to obtain low-odor polypropylene grafted maleic anhydride beads;
the monomer is selected from one or more of styrene, cyclopentadiene and thiuram;
the initiator is selected from one or more of benzoyl peroxide, di-tert-butylperoxyisopropyl benzene, 2, 3-dimethyl-2, 3-diphenyl butane and 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane.
2. The method according to claim 1, wherein the pressure for injecting the supercritical carbon dioxide is 7.38 to 10.0 MPa.
3. The method of claim 1, wherein the antioxidant is selected from one or more of hindered phenolic antioxidants, phosphite antioxidants, and thioester antioxidants.
4. The method of claim 1, wherein the polypropylene is selected from the group consisting of isotactic polypropylene;
the melt flow index of the polypropylene is 1-50 g/10 min.
5. The method of claim 1, wherein the supercritical carbon dioxide is added at 1-5% of the polypropylene feed rate.
6. The method according to claim 1, characterized in that the preparation is carried out in a twin-screw extruder;
the double-screw extruder is provided with 12 sections from a feed opening to a heating zone of a machine head, and the sections are sequentially set to 160-170 ℃, 170-190 ℃, 160-195 ℃, 160-210 ℃, 160-220 ℃, 160-210 ℃, the screw rotating speed is 150-400 r/min, and the feeding rotating speed is 10-50 kg/h.
7. The method of claim 1, wherein the low-odor polypropylene grafted maleic anhydride beads have a length of 1 to 1.5mm and a diameter of 0.5 to 1.5 mm.
8. The method according to claim 1, wherein 100 parts of polypropylene, 1.2 parts of maleic anhydride, 1.2 parts of styrene, 0.2 part of antioxidant, and 0.1 part of di-tert-butylperoxyisopropyl benzene; the pressure for injecting the supercritical carbon dioxide is 7.5 MPa;
or 100 parts of polypropylene resin, 0.2 part of antioxidant, 1.2 parts of maleic anhydride, 1.0 part of styrene and 0.1 part of di-tert-butylperoxyisopropyl benzene; the pressure for injecting the supercritical carbon dioxide is 7.5 MPa;
or 100 parts of polypropylene resin, 0.2 part of antioxidant, 1.5 parts of maleic anhydride, 1.3 parts of styrene and 0.15 part of di-tert-butylperoxyisopropyl benzene; the pressure for injecting the supercritical carbon dioxide was 7.5 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111433284.XA CN113968940A (en) | 2021-11-29 | 2021-11-29 | Method for preparing low-odor polypropylene grafted maleic anhydride beads under assistance of supercritical carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111433284.XA CN113968940A (en) | 2021-11-29 | 2021-11-29 | Method for preparing low-odor polypropylene grafted maleic anhydride beads under assistance of supercritical carbon dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113968940A true CN113968940A (en) | 2022-01-25 |
Family
ID=79590296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111433284.XA Pending CN113968940A (en) | 2021-11-29 | 2021-11-29 | Method for preparing low-odor polypropylene grafted maleic anhydride beads under assistance of supercritical carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113968940A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073672A (en) * | 2022-06-28 | 2022-09-20 | 山东京博石油化工有限公司 | Low-odor POE (polyolefin elastomer) grafted maleic anhydride as well as preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1486998A (en) * | 2003-07-24 | 2004-04-07 | 华东理工大学 | Supercritical CO2 medium process of preparing unsaturated organic acid grafted polypropylene |
| CN102837408A (en) * | 2012-09-18 | 2012-12-26 | 贵州凯科特材料有限公司 | Double screw extruder and method for using same to prepare light-smell polypropylene |
| CN104292392A (en) * | 2014-09-26 | 2015-01-21 | 宁波能之光新材料科技有限公司 | Preparation method of high-purity grafted functionalized copolymer |
-
2021
- 2021-11-29 CN CN202111433284.XA patent/CN113968940A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1486998A (en) * | 2003-07-24 | 2004-04-07 | 华东理工大学 | Supercritical CO2 medium process of preparing unsaturated organic acid grafted polypropylene |
| CN102837408A (en) * | 2012-09-18 | 2012-12-26 | 贵州凯科特材料有限公司 | Double screw extruder and method for using same to prepare light-smell polypropylene |
| CN104292392A (en) * | 2014-09-26 | 2015-01-21 | 宁波能之光新材料科技有限公司 | Preparation method of high-purity grafted functionalized copolymer |
Non-Patent Citations (1)
| Title |
|---|
| 曲邦威: "超临界反应挤出法制备改性聚丙烯", 《中国优秀硕士学位论文全文数据库》, no. 09, pages 23 - 24 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073672A (en) * | 2022-06-28 | 2022-09-20 | 山东京博石油化工有限公司 | Low-odor POE (polyolefin elastomer) grafted maleic anhydride as well as preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112048124B (en) | Glass fiber reinforced polypropylene material with low-floating-fiber surface and preparation method thereof | |
| CN109456563B (en) | Special material for UHMWPE alloy compatibilization toughening modified polypropylene corrugated pipe and preparation method thereof | |
| WO2018218647A1 (en) | Thermoplastic composite, method of making thermoplastic composite, and injection-molded product | |
| CN109401243A (en) | A kind of high-ductility biological poly lactic acid/response type modified rubber thermoplastic sulfurized rubber intermingling material and its secondary response squeeze out preparation method | |
| CN109081894B (en) | High-fluidity toughening agent and preparation method thereof | |
| CN111471245A (en) | Polystyrene composite material and preparation method thereof | |
| CN113968940A (en) | Method for preparing low-odor polypropylene grafted maleic anhydride beads under assistance of supercritical carbon dioxide | |
| CN111825801B (en) | Toughening agent composition and preparation method thereof | |
| CN114369347A (en) | Degradable flow modification auxiliary agent and preparation method and application thereof | |
| CN107383744B (en) | Polypropylene modified material for waste household appliances and preparation method thereof | |
| CN107513132A (en) | A kind of high melt strength polypropylene material and preparation method thereof | |
| CN110734630A (en) | high-toughness PET material for plastic uptake box | |
| CN115109194B (en) | Polyethylene grafted maleic anhydride hot melt adhesive modified material and preparation method thereof | |
| CN114933878B (en) | Strong plastic-lined metal pipe quick adhesive and preparation method thereof | |
| CN103694613B (en) | A kind of low floating fine fiberglass reinforced toughened polypropylene composite and preparation method thereof | |
| CN107540935B (en) | Polypropylene reclaimed material composition and preparation method thereof | |
| CN109971164B (en) | Modified PA composite material and preparation method thereof | |
| CN110483889B (en) | Rotational molding polypropylene alloy material and preparation method thereof | |
| CN107141733A (en) | A kind of ABS strengthens modified PBT composition | |
| CN111825802B (en) | Ethylene oxide-octene copolymer composition and preparation method thereof | |
| CN110760124B (en) | Glass fiber waste silk reinforced polypropylene composite material and preparation method thereof | |
| CN102276848B (en) | Method for modifying and pretreating bacterium mushroom stick used for preparing wood-plastic composite material | |
| CN104672796A (en) | High-performance low-cost PET/ABS composite material and preparation method thereof | |
| CN110684277B (en) | Low-temperature-resistant waste PP/LDPE composite material and preparation method thereof | |
| CN113897044B (en) | PC/EVA composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |