CN102731905A - Long glass fiber reinforced modified polypropylene and preparation method thereof - Google Patents
Long glass fiber reinforced modified polypropylene and preparation method thereof Download PDFInfo
- Publication number
- CN102731905A CN102731905A CN2012101585564A CN201210158556A CN102731905A CN 102731905 A CN102731905 A CN 102731905A CN 2012101585564 A CN2012101585564 A CN 2012101585564A CN 201210158556 A CN201210158556 A CN 201210158556A CN 102731905 A CN102731905 A CN 102731905A
- Authority
- CN
- China
- Prior art keywords
- long glass
- glass fibres
- enhancing modified
- preparation
- long
- 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.)
- Granted
Links
- 239000003365 glass fiber Substances 0.000 title claims abstract description 105
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 63
- -1 polypropylene Polymers 0.000 title claims abstract description 32
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000004381 surface treatment Methods 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 230000002708 enhancing effect Effects 0.000 claims description 34
- 239000004925 Acrylic resin Substances 0.000 claims description 29
- 229920000178 Acrylic resin Polymers 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000011521 glass Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 13
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 229920000768 polyamine Polymers 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003595 mist Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 238000009434 installation Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 208000031737 Tissue Adhesions Diseases 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The present invention discloses a long glass fiber reinforced modified polypropylene. The polypropylene is prepared from the following components, by mass, 60-80% of a polypropylene resin, 10-30% of long glass fiber, 2-5% of a processing additive, 1-3% of a compatibilizer, and 1-5% of PA6. Mechanical performance and thermal performance of the polypropylene of the present invention are substantially improved. The present invention further discloses a preparation method for the long glass fiber reinforced modified polypropylene. According to the method, a surface treatment is performed on long glass fiber; and the surface-treated long glass fiber is added to a twin-screw extruder, and is subjected to blending modification with the molten polypropylene resin to obtain the reinforced modified polypropylene with the long length glass fiber in the interior. The preparation process is simple, no special equipment is required, and the method is suitable for factory production.
Description
Technical field
The present invention relates to thermal plastic high polymer chemical material field, especially relate to a kind of long glass fibres enhancing modified Vestolen PP 7052 and preparation method thereof.
Background technology
Vestolen PP 7052 (pp) is that a kind of cost is low, excellent performance, broad-spectrum macromolecular material; Because it is filling-modified that it is easy to carry out, and after modification, can improve mechanical property, and corrosion-resistant; Therefore Vestolen PP 7052 becomes resin material very widely, especially at automobile manufacturing field.
In recent years, glass-reinforced polypropylene has a wide range of applications, for example; Chinese patent publication number CN101381492A; Open day: disclosed a kind of polypropylene composite material and preparation method thereof on March 11st, 2009, this polypropylene composite material contained acrylic resin, spun glass and oxidation inhibitor; Wherein, the staple length of said spun glass is 0.4 ~ 1MM.Glass fibre length in this matrix material has only 0.4 ~ 1MM, belongs to short glass fiber, though improved polyacrylic mechanical property to a certain extent, its mechanical property and toughness are still relatively poor, and thermal property is also relatively poor, and machine-shaping property is relatively poor.
Consumption through improving spun glass in the PP composite material all can improve its mechanical property and toughness; But the consumption that directly improves spun glass can increase production cost; The reservation length that improves spun glass also can improve the mechanical property and the toughness of PP composite material, but the consistency of spun glass and acrylic resin is relatively poor, in the preparation process, is prone to rupture; Be difficult for keeping the length of length; Therefore, how in the process of preparation glass-reinforced polypropylene, to improve the consistency of spun glass and acrylic resin, reduce the damage of spun glass in preparation and the moulding process; Thereby, be mechanical property and the key issue of flexible that improves glass-reinforced polypropylene to improve the reservation length of spun glass.
Summary of the invention
The objective of the invention is in order to solve the relatively poor problem of glass-reinforced polypropylene mechanical property, toughness and thermal property of prior art; It is long to provide a kind of spun glass to keep length, and the long glass fibres enhancing modified Vestolen PP 7052 that is improved significantly of mechanical property and thermal property.
The present invention also provides a kind of long glass fibres enhancing modified polyacrylic preparation method, and this preparing method's technology is simple, need not specific installation, is fit to batch production production.
To achieve these goals, the present invention adopts following technical scheme:
A kind of long glass fibres enhancing modified Vestolen PP 7052, process by the component of following mass percent: acrylic resin 60 ~ 80%, the long glass fibres 10 ~ 30% after surface treatment, processing aid 2 ~ 5%, compatilizer 1 ~ 3%, PA6 1 ~ 5%.The acrylic resin price is low, good processability, but mechanical property is relatively poor; And PA6 has excellent heat resisting and mechanical property, therefore in acrylic resin, add PA6, but the consistency of PA6 and acrylic resin is relatively poor; Therefore be added with compatilizer to improve the consistency of PA6 and acrylic resin; Make Vestolen PP 7052 have acrylic resin good processing properties and PA6 excellent thermotolerance and mechanical property concurrently through blending and modifying, add long glass fibres after surface treatment simultaneously, make it have better mechanical property to improve polyacrylic toughness; The polyacrylic mechanical property of long glass fibres enhancing modified improves with the increase of the long glass fibres content after surface treatment wherein; But if the long glass content after surface treatment is lower than 10% in the long glass fibres enhancing modified Vestolen PP 7052, then the overall mechanical property raising of Vestolen PP 7052 is not obvious, if the long glass fibres content after surface treatment surpasses 30% in the long glass fibres enhancing modified Vestolen PP 7052; Can cause the resin of long glass fibres enhancing modified Vestolen PP 7052 inside between the long glass fibres after the surface treatment very few again; Produce the cavity, when causing the acrylic resin matrix stressed its inside between the long glass fibres after the surface treatment, be prone to peel off, unsticking, the while is in moulding process; Between the long glass fibres after the surface treatment, be prone to rub; Cause the long glass fibres damage after surface treatment, make length descend, so the content of long glass fibres is long glass fibres 10 ~ 30% among the present invention; The present invention is processed by the component of above-mentioned mass percent, and its mechanical property and thermal property all can be improved significantly.
As preferably, described long glass fibres length after surface treatment is 6 ~ 15mm.Glass fibre length among the present invention after surface treatment reaches 6 ~ 15mm, can improve the mechanical property and the toughness of PP composite material greatly.
As preferably, described acrylic resin is made up of the component of following mass percent: HOPP 30 ~ 40%, atactic copolymerized polypropene 60 ~ 70%.Acrylic resin is mixed by 30 ~ 40% HOPP and 60 ~ 70% atactic copolymerized polypropene, when keeping performance to reduce cost.
As preferably; Described processing aid is made up of the component of following mass percent: oxidation inhibitor 10 ~ 15%, photostabilizer 10 ~ 15%, dispersion agent 70 ~ 80%; Wherein, Described oxidation inhibitor is IRGANOX B 225, and described photostabilizer is Tinuvin 783, and described dispersion agent is HONEYWELL ACumist A-6.
Processing aid among the present invention forms by oxidation inhibitor, photostabilizer and dispersion agent are composite, adds processing aid to improve the polyacrylic processing characteristics of long glass fibres enhancing modified, and oxidation inhibitor can be all kinds of compound antioxidants; Mainly prevent the oxidation of polymkeric substance in the preparation process; Preferred IRGANOX B 225, photostabilizer can be all kinds of hindered amine as light stabilizer, mainly prevents the light-heat aging of acrylic resin; Preferred Tinuvin 783; Dispersion agent is the micronization OPE, mainly is the effect of antisolvent precipitation and tissue adhesion, preferred HONEYWELL ACumist A-6.
As preferably, described compatilizer is that percentage of grafting is 0.8 ~ 1% maleic anhydride inoculated polypropylene.The adding maleic anhydride inoculated polypropylene can improve the interface bonding of polypropylene matrix and strongthener in acrylic resin, and percentage of grafting is 0.8 ~ 1% maleic anhydride inoculated polypropylene, improves the effective of interface adhesion.
The polyacrylic preparation method of a kind of long glass fibres enhancing modified may further comprise the steps:
(a) in long glass fibres enhancing modified Vestolen PP 7052 total mass, the acrylic resin with 60 ~ 80%, 2 ~ 5% processing aid, 1 ~ 3% compatilizer and 1 ~ 5% PA6 add high-speed mixer and mix, and obtain compound.
(b) compound is added twin screw extruder,, obtain melt blended material at 210 ~ 220 ℃ of melt blendings.Adopt the crowded function of twin screw to make through the long glass fibres after the surface treatment and in acrylic resin, be uniformly dispersed, damage is also less when extruding simultaneously, helps the reservation length that keeps long.
(c) in long glass fibres enhancing modified Vestolen PP 7052 total mass; 10 ~ 30% long glass fibress after surface treatment are added twin screw extruder; Extrude behind 220 ~ 230 ℃ of melt blendings with melt blended material, obtain long glass fibres enhancing modified Vestolen PP 7052.Employing is carried out surface treatment to long glass fibres, can effectively improve interface binding intensity and the processing characteristics of long glass fibres between long glass fibres and the acrylic resin, reduces the damage of long glass fibres in the preparation process simultaneously; It enables to have long reservation length; In addition, adopt the mixing technology of directly extruding, promptly directly the long glass fibres after surface treatment is added twin screw extruder; Carry out blending and modifying with fused acrylic resin; Under the shearing action of twin screw extruder screw rod, the long glass fibres after surface treatment cuts into certain length and mixes with acrylic resin, just can obtain inside after extruding and contain the long RPP that keeps the length spun glass; This preparation technology is simple, need not specific installation.
As preferably, the surface-treated method is in the step (c): long glass fibres is soaked in treating compound behind 10 ~ 30min in 95 ~ 105 ℃ of oven dry down.Soak through treating compound; Make the long glass fibres surface energy after drying form the protective membrane of layer of protecting spun glass, can reduce its damage and weathering in subsequent preparation process, thereby guarantee that long glass fibres has long reservation length; In addition; Long glass fibres surfaceness through soaking also becomes greatly, can make the more chemical bond of formation between long glass fibres and the acrylic resin, the frictional coefficient between increase and the acrylic resin; Thereby interface shear strength is increased, improved toughness.
As preferably, described long glass fibres is the alkali-free continuous glass fibre of diameter 17 μ m.The alkali-free continuous glass fibre has long length, and surfaceness is bigger, helps improving the interface shear strength between long glass fibres and the acrylic resin, improves toughness.
As preferably, described treating compound is made up of the component of following weight percent: water soluble resin 1 ~ 5%, and urea-formaldehyde resin 0.2 ~ 1%, glass lubricant 2 ~ 5%, silane coupling agent 0.1 ~ 0.5%, all the other are water, wherein, described silane coupling agent is KH – 570.This treating compound is contriver's self-control; Through this treating compound long glass fibres is soaked; Make that the long glass fibres filament strength after soaking into is high, toughness is strengthened, not easy fracture; The reservation length of long glass fibres in acrylic resin be can increase, thereby polyacrylic mechanical property of long glass fibres enhancing modified and toughness improved.
As preferably; Described water soluble resin is made by following method: 4 ~ 4.5mol Ucar 35,0.5 ~ 1mol hexanodioic acid, 1 ~ 2mol Tetra hydro Phthalic anhydride and 1.5 ~ 2.5mol MALEIC ANHYDRIDE are added in the four-hole reaction kettle simultaneously; Add quality again and be 0.1 ~ 0.5% tosic acid of Ucar 35, hexanodioic acid, Tetra hydro Phthalic anhydride and MALEIC ANHYDRIDE total mass, at N
2Being heated to 80 ~ 100 ℃ under the protection all melts reactant; Open stirring again and be warming up to 190 ~ 210 ℃, behind insulation 3 ~ 5h, add 4 ~ 5mol terepthaloyl moietie when being cooled to 90 ~ 100 ℃; When continuing to be stirred to 50 ~ 80 ℃; Add 0.5 ~ 1mol monoethanolamine and 0.5 ~ 1mol polyethylene polyamine simultaneously, finish that to be stirred to solution transparent, add Glacial acetic acid min. 99.5 regulator solution pH to 5 ~ 7 at last and promptly get water soluble resin.Ucar 35 and hexanodioic acid in the time of 190 ~ 210 ℃ and the catalyzer tosic acid in the presence of the dehydration polymerization can take place forms the linear macromolecule polyester, add Tetra hydro Phthalic anhydride and MALEIC ANHYDRIDE to obtain to contain the unsaturated polyester of the two keys of certain number C=C, increase the functional group of difference in functionality simultaneously; With the consistency of raising with long glass fibres; Unsaturated polyester can obtain a kind of water miscible amido polyester with monoethanolamine, polyethylene polyamine generation addition again, and glacial acetic acid is with the alkalescence in the neutralization reaction system, the gelling of cis-butenedioic anhydride excessive meeting causing resin; Need its consumption of control; Therefore the add-on of MALEIC ANHYDRIDE is 1.5 ~ 2.5mol, and the increase of phthalic anhydride consumption can be avoided the resin gelling, but excessive phthalic anhydride can reduce the water-soluble of resin; Be unfavorable for the preparation and the application of treating compound, so the consumption of Tetra hydro Phthalic anhydride is controlled at 1 ~ 2mol.
Therefore, the present invention has following beneficial effect:
(1) mechanical property and thermal property are improved significantly;
(2) preparing method's technology is simple, need not specific installation, is fit to batch production production.
Embodiment
Through specific embodiment technical scheme of the present invention is further specified below.Should be appreciated that enforcement of the present invention is not limited to following embodiment, all will fall into protection domain of the present invention any pro forma accommodation and/or the change that the present invention made.
In following examples, if there is not explanation, all raw materials etc. all can be buied from market or the industry is commonly used; Wherein, Long glass fibres is available from Jushi Group Co., Ltd., and HOPP is available from chemical industry difficult to understand (Hong Kong) ltd of Dongguan City profit, and atactic copolymerized polypropene is available from raising sub-petrochemical industry limited-liability company; Maleic anhydride inoculated polypropylene is available from the light company of Ningbo ability; IRGANOX B 225 is available from the Switzerland Ciba ltd that refines, and Tinuvin 783 gushes dark trade Co., Ltd available from Ningbo Hai Shu, and HONEYWELL ACumist A-6 is available from Wuxi Suo Fei rowland International Trading Company Ltd; Urea-formaldehyde resin is available from Leqing, Zhejiang Province resin processing plant; Glass lubricant is available from Hangzhou Bai Shan spun glass auxiliary agent ltd, and KH – 570 joins silication worker ltd available from Nanjing, and polyethylene polyamine is available from Gutian, Nanjing chemical industry ltd.
Embodiment 1
In long glass fibres enhancing modified Vestolen PP 7052 total mass, take by weighing each component by the mass percent shown in the table 1, acrylic resin, processing aid, compatilizer and PA6 adding high-speed mixer are mixed obtain compound earlier; Obtain melt blended material at 210 ℃ of melt blendings after then compound being added twin screw extruder; Again the long glass fibres after surface treatment is added twin screw extruder; The surface-treated method is: dry down in 95 ℃ long glass fibres is soaked 30min in treating compound after; Long glass fibres is the alkali-free continuous glass fibre of diameter 17 μ m; Treating compound is made up of water soluble resin, urea-formaldehyde resin, glass lubricant, silane coupling agent and water; The mass percent of each component is as shown in table 2, and wherein, water soluble resin makes through following method: 4.2mol Ucar 35,1mol hexanodioic acid, 1.5mol Tetra hydro Phthalic anhydride and 1.5mol MALEIC ANHYDRIDE are added in the four-hole reaction kettle simultaneously; Add quality again and be 0.3% tosic acid of Ucar 35, hexanodioic acid, Tetra hydro Phthalic anhydride and MALEIC ANHYDRIDE total mass, at N
2Being heated to 100 ℃ under the protection all melts reactant; Open stirring again and be warming up to 210 ℃; Behind the insulation 5h, add 5mol terepthaloyl moietie when being cooled to 90 ℃, add 1mol monoethanolamine and 0.7mol polyethylene polyamine when continuing to be stirred to 60 ℃ simultaneously; Finish that to be stirred to solution transparent, add glacial acetic acid regulator solution pH to 5 and promptly get water soluble resin; After long glass fibres after the surface treatment and melt blended material are extruded, obtain long glass fibres enhancing modified Vestolen PP 7052 behind 220 ℃ of melt blendings.
Long glass fibres enhancing modified Vestolen PP 7052 to obtaining carries out performance test, and the result who obtains is as shown in table 3.
Embodiment 2
In long glass fibres enhancing modified Vestolen PP 7052 total mass, take by weighing each component by the mass percent shown in the table 1, acrylic resin, processing aid, compatilizer and PA6 adding high-speed mixer are mixed obtain compound earlier; Obtain melt blended material at 215 ℃ of melt blendings after then compound being added twin screw extruder; Again the long glass fibres after surface treatment is added twin screw extruder; The surface-treated method is: dry down in 100 ℃ long glass fibres is soaked 10min in treating compound after; Long glass fibres is the alkali-free continuous glass fibre of diameter 17 μ m; Treating compound is made up of water soluble resin, urea-formaldehyde resin, glass lubricant, silane coupling agent and water; The mass percent of each component is as shown in table 2, and wherein, water soluble resin makes through following method: 4.5mol Ucar 35,0.5mol hexanodioic acid, 1mol Tetra hydro Phthalic anhydride and 2.5mol MALEIC ANHYDRIDE are added in the four-hole reaction kettle simultaneously; Add quality again and be 0.1% tosic acid of Ucar 35, hexanodioic acid, Tetra hydro Phthalic anhydride and MALEIC ANHYDRIDE total mass, at N
2Being heated to 80 ℃ under the protection all melts reactant; Open stirring again and be warming up to 200 ℃; Behind the insulation 4h, add 4mol terepthaloyl moietie when being cooled to 100 ℃, add 0.5mol monoethanolamine and 0.5mol polyethylene polyamine when continuing to be stirred to 50 ℃ simultaneously; Finish that to be stirred to solution transparent, add glacial acetic acid regulator solution pH to 6 and promptly get water soluble resin; After long glass fibres after the surface treatment and melt blended material are extruded, obtain long glass fibres enhancing modified Vestolen PP 7052 behind 230 ℃ of melt blendings.
Long glass fibres enhancing modified Vestolen PP 7052 to obtaining carries out performance test, and the result who obtains is as shown in table 3.
Embodiment 3
In long glass fibres enhancing modified Vestolen PP 7052 total mass, take by weighing each component by the mass percent shown in the table 1, acrylic resin, processing aid, compatilizer and PA6 adding high-speed mixer are mixed obtain compound earlier; Obtain melt blended material at 220 ℃ of melt blendings after then compound being added twin screw extruder; Again the long glass fibres after surface treatment is added twin screw extruder; The surface-treated method is: dry down in 105 ℃ long glass fibres is soaked 15min in treating compound after; Long glass fibres is the alkali-free continuous glass fibre of diameter 17 μ m; Treating compound is made up of water soluble resin, urea-formaldehyde resin, glass lubricant, silane coupling agent and water; The mass percent of each component is as shown in table 2, and wherein, water soluble resin makes through following method: 4mol Ucar 35,0.6mol hexanodioic acid, 2mol Tetra hydro Phthalic anhydride and 1.8mol MALEIC ANHYDRIDE are added in the four-hole reaction kettle simultaneously; Add quality again and be 0.5% tosic acid of Ucar 35, hexanodioic acid, Tetra hydro Phthalic anhydride and MALEIC ANHYDRIDE total mass, at N
2Being heated to 90 ℃ under the protection all melts reactant; Open stirring again and be warming up to 190 ℃; Behind the insulation 3h, add 4mol terepthaloyl moietie when being cooled to 95 ℃, add 0.6mol monoethanolamine and 1mol polyethylene polyamine when continuing to be stirred to 80 ℃ simultaneously; Finish that to be stirred to solution transparent, add glacial acetic acid regulator solution pH to 7 and promptly get water soluble resin; After long glass fibres after the surface treatment and melt blended material are extruded, obtain long glass fibres enhancing modified Vestolen PP 7052 behind 225 ℃ of melt blendings.
Long glass fibres enhancing modified Vestolen PP 7052 to obtaining carries out performance test, and the result who obtains is as shown in table 3.
Comparative Examples
With the object as a comparison of the golden hair GFPP-L30 NC007 on the market, it is carried out performance test, the result who obtains is as shown in table 3.
Polyacrylic each constituent mass per-cent of long glass fibres enhancing modified among table 1 embodiment
Each constituent mass per-cent of treating compound among each embodiment of table 2
The The performance test results of table 3 embodiment and Comparative Examples
Can find out from table 3; Contain the long glass fiber reinforced polypropylene that mass percent is 24% the long glass fibres after surface treatment among the present invention; Its mechanical property and thermal property have just reached the mechanical property and the thermal property of the long glass fiber reinforced polypropylene of the long glass fibres that contains mass percent 30% on the market; And contain the long glass fiber reinforced polypropylene that mass percent is 30% the long glass fibres after surface treatment among the present invention; Its mechanical property and thermal property obviously surpass the mechanical property and the thermal property of the long glass fiber reinforced polypropylene of the long glass fibres that contains equal in quality percentage ratio on the market, mechanical property and hot being significantly improved that long glass fiber reinforced polypropylene of the present invention is described.
Claims (10)
1. a long glass fibres enhancing modified Vestolen PP 7052 is characterized in that, is processed by the component of following mass percent: acrylic resin 60 ~ 80%, and the long glass fibres 10 ~ 30% after surface treatment, processing aid 2 ~ 5%, compatilizer 1 ~ 3%, PA6 1 ~ 5%.
2. a kind of long glass fibres enhancing modified Vestolen PP 7052 according to claim 1 is characterized in that described long glass fibres length after surface treatment is 6 ~ 15mm.
3. a kind of long glass fibres enhancing modified Vestolen PP 7052 according to claim 1 is characterized in that described acrylic resin is made up of the component of following mass percent: HOPP 30 ~ 40%, atactic copolymerized polypropene 60 ~ 70%.
4. according to claim 1 or 3 described a kind of long glass fibres enhancing modified Vestolen PP 7052, it is characterized in that described processing aid is made up of the component of following mass percent: oxidation inhibitor 10 ~ 15%; Photostabilizer 10 ~ 15%; Dispersion agent 70 ~ 80%, wherein, described oxidation inhibitor is IRGANOX B 225; Described photostabilizer is Tinuvin 783, and described dispersion agent is HONEYWELL AC μ mist A-6.
5. a kind of long glass fibres enhancing modified Vestolen PP 7052 according to claim 4 is characterized in that, described compatilizer is that percentage of grafting is 0.8 ~ 1% maleic anhydride inoculated polypropylene.
6. the polyacrylic preparation method of long glass fibres enhancing modified as claimed in claim 1 is characterized in that, may further comprise the steps:
In long glass fibres enhancing modified Vestolen PP 7052 total mass, the acrylic resin with 60 ~ 80%, 2 ~ 5% processing aid, 1 ~ 3% compatilizer and 1 ~ 5% PA6 add high-speed mixer and mix, and obtain compound;
Compound is added twin screw extruder,, obtain melt blended material at 210 ~ 220 ℃ of melt blendings;
In long glass fibres enhancing modified Vestolen PP 7052 total mass, 10 ~ 30% long glass fibress after surface treatment are added twin screw extruder, extrude behind 220 ~ 230 ℃ of melt blendings with melt blended material, obtain long glass fibres enhancing modified Vestolen PP 7052.
7. preparation method according to claim 6 is characterized in that, the surface-treated method is in the step (c): dry down in 95 ~ 105 ℃ long glass fibres is soaked 10 ~ 30min in treating compound after.
8. according to claim 6 or 7 described preparing methods, it is characterized in that described long glass fibres is the alkali-free continuous glass fibre of diameter 17 μ m.
9. preparation method according to claim 7 is characterized in that, described treating compound is made up of the component of following weight percent: water soluble resin 1 ~ 5%; Urea-formaldehyde resin 0.2 ~ 1%; Glass lubricant 2 ~ 5%, silane coupling agent 0.1 ~ 0.5%, all the other are water; Wherein, described silane coupling agent is KH – 570.
10. preparation method according to claim 9; It is characterized in that; Described water soluble resin is made by following method: 4 ~ 4.5mol Ucar 35,0.5 ~ 1mol hexanodioic acid, 1 ~ 2mol Tetra hydro Phthalic anhydride and 1.5 ~ 2.5mol MALEIC ANHYDRIDE are added in the four-hole reaction kettle simultaneously; Add quality again and be 0.1 ~ 0.5% tosic acid of Ucar 35, hexanodioic acid, Tetra hydro Phthalic anhydride and MALEIC ANHYDRIDE total mass, at N
2Being heated to 80 ~ 100 ℃ under the protection all melts reactant; Open stirring again and be warming up to 190 ~ 210 ℃, behind insulation 3 ~ 5h, add 4 ~ 5mol terepthaloyl moietie when being cooled to 90 ~ 100 ℃; When continuing to be stirred to 50 ~ 80 ℃; Add 0.5 ~ 1mol monoethanolamine and 0.5 ~ 1mol polyethylene polyamine simultaneously, finish that to be stirred to solution transparent, add Glacial acetic acid min. 99.5 regulator solution pH to 5 ~ 7 at last and promptly get water soluble resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210158556.4A CN102731905B (en) | 2012-05-22 | 2012-05-22 | Long glass fiber reinforced modified polypropylene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210158556.4A CN102731905B (en) | 2012-05-22 | 2012-05-22 | Long glass fiber reinforced modified polypropylene and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102731905A true CN102731905A (en) | 2012-10-17 |
| CN102731905B CN102731905B (en) | 2014-04-09 |
Family
ID=46988254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210158556.4A Active CN102731905B (en) | 2012-05-22 | 2012-05-22 | Long glass fiber reinforced modified polypropylene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102731905B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113667A (en) * | 2012-12-26 | 2013-05-22 | 江苏金发科技新材料有限公司 | Continuous long glass fiber reinforced polypropylene/nylon composite material with core layer structure and preparation process thereof |
| CN103194021A (en) * | 2013-04-10 | 2013-07-10 | 苏州旭光聚合物有限公司 | High-temperature resistant glass fiber reinforced polypropylene and production method thereof |
| CN103289375A (en) * | 2013-05-22 | 2013-09-11 | 江苏金发科技新材料有限公司 | Continuous glass fiber reinforced polypropylene-nylon composite material and preparation method thereof |
| CN103613853A (en) * | 2013-11-13 | 2014-03-05 | 深圳市科聚新材料有限公司 | Transparent glass fiber reinforced polypropylene (PP) composite material and preparation method thereof |
| CN103849141A (en) * | 2012-12-06 | 2014-06-11 | 上海杰事杰新材料(集团)股份有限公司 | Long glassfiber reinforced nylon composite material and preparation method thereof |
| CN103881236A (en) * | 2014-03-10 | 2014-06-25 | 洛阳市河之阳高分子材料有限公司 | Polypropylene material used for lithium battery shell and preparation method thereof |
| CN105924777A (en) * | 2016-05-25 | 2016-09-07 | 河北立格环保科技股份有限公司 | Long fiber reinforced thermoplastic composite material and application thereof |
| CN106280239A (en) * | 2016-08-08 | 2017-01-04 | 苏州极地实业有限公司 | A kind of construction decoration composite |
| CN106750960A (en) * | 2016-12-27 | 2017-05-31 | 上海普利特复合材料股份有限公司 | A kind of high-intensity high-tenacity continuous glass-fiber RPP sheet material and preparation method thereof |
| CN108102276A (en) * | 2017-12-11 | 2018-06-01 | 许水仙 | A kind of preparation method of high strength starch plastics |
| CN109164106A (en) * | 2018-09-25 | 2019-01-08 | 巨石集团有限公司 | Glass retains the test method of length in fiberglass reinforced thermoplastic composite |
| CN109666216A (en) * | 2018-12-17 | 2019-04-23 | 会通新材料(上海)有限公司 | A kind of long glass fiber-reinforced polypropylene/polyamide alloy material and preparation method thereof of high-intensitive, low smell |
| CN110818999A (en) * | 2019-09-30 | 2020-02-21 | 广东轻工职业技术学院 | High weld mark strength glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN114507400A (en) * | 2020-10-27 | 2022-05-17 | 合肥杰事杰新材料股份有限公司 | Modified glass fiber reinforced polypropylene composition and preparation method thereof |
| CN116041841A (en) * | 2022-11-21 | 2023-05-02 | 福建易安特新型建材有限公司 | Glass fiber reinforced modified polypropylene resin and mixing device thereof |
| CN117153470A (en) * | 2023-08-29 | 2023-12-01 | 江苏荣宜电缆有限公司 | Waterproof anti-aging photovoltaic cable and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090311458A1 (en) * | 2006-12-19 | 2009-12-17 | Basell Poliolefine Italia S.R.L. | Multilayer laminated material having at least one glass layer |
| CN102146184A (en) * | 2011-04-22 | 2011-08-10 | 威海联桥新材料科技股份有限公司 | High-gloss fatigue-resistance glass fiber reinforced PP (propene polymer) /PPR (pentatricopeptide repeats) /PA (polyamide) alloy material and production method thereof |
| CN102167867A (en) * | 2011-05-18 | 2011-08-31 | 合肥会通新材料有限公司 | Continuous glass fiber reinforced polypropylene/nylon alloy chopped material and preparation method thereof |
-
2012
- 2012-05-22 CN CN201210158556.4A patent/CN102731905B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090311458A1 (en) * | 2006-12-19 | 2009-12-17 | Basell Poliolefine Italia S.R.L. | Multilayer laminated material having at least one glass layer |
| CN102146184A (en) * | 2011-04-22 | 2011-08-10 | 威海联桥新材料科技股份有限公司 | High-gloss fatigue-resistance glass fiber reinforced PP (propene polymer) /PPR (pentatricopeptide repeats) /PA (polyamide) alloy material and production method thereof |
| CN102167867A (en) * | 2011-05-18 | 2011-08-31 | 合肥会通新材料有限公司 | Continuous glass fiber reinforced polypropylene/nylon alloy chopped material and preparation method thereof |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103849141A (en) * | 2012-12-06 | 2014-06-11 | 上海杰事杰新材料(集团)股份有限公司 | Long glassfiber reinforced nylon composite material and preparation method thereof |
| CN103113667B (en) * | 2012-12-26 | 2016-05-18 | 江苏金发科技新材料有限公司 | There is continuous long glass fiber reinforced profax/nylon composite materials and the preparation technology thereof of core structure |
| CN103113667A (en) * | 2012-12-26 | 2013-05-22 | 江苏金发科技新材料有限公司 | Continuous long glass fiber reinforced polypropylene/nylon composite material with core layer structure and preparation process thereof |
| CN103194021A (en) * | 2013-04-10 | 2013-07-10 | 苏州旭光聚合物有限公司 | High-temperature resistant glass fiber reinforced polypropylene and production method thereof |
| CN103289375A (en) * | 2013-05-22 | 2013-09-11 | 江苏金发科技新材料有限公司 | Continuous glass fiber reinforced polypropylene-nylon composite material and preparation method thereof |
| CN103613853A (en) * | 2013-11-13 | 2014-03-05 | 深圳市科聚新材料有限公司 | Transparent glass fiber reinforced polypropylene (PP) composite material and preparation method thereof |
| CN103613853B (en) * | 2013-11-13 | 2016-06-01 | 深圳市科聚新材料有限公司 | A kind of transparent glass fiber reinforced polypropylene compound material and its preparation method |
| CN103881236A (en) * | 2014-03-10 | 2014-06-25 | 洛阳市河之阳高分子材料有限公司 | Polypropylene material used for lithium battery shell and preparation method thereof |
| CN105924777B (en) * | 2016-05-25 | 2018-07-06 | 河北立格新材料科技股份有限公司 | A kind of long fiber reinforced thermoplastic composites and its application |
| CN105924777A (en) * | 2016-05-25 | 2016-09-07 | 河北立格环保科技股份有限公司 | Long fiber reinforced thermoplastic composite material and application thereof |
| CN106280239A (en) * | 2016-08-08 | 2017-01-04 | 苏州极地实业有限公司 | A kind of construction decoration composite |
| CN106750960A (en) * | 2016-12-27 | 2017-05-31 | 上海普利特复合材料股份有限公司 | A kind of high-intensity high-tenacity continuous glass-fiber RPP sheet material and preparation method thereof |
| CN108102276A (en) * | 2017-12-11 | 2018-06-01 | 许水仙 | A kind of preparation method of high strength starch plastics |
| CN109164106A (en) * | 2018-09-25 | 2019-01-08 | 巨石集团有限公司 | Glass retains the test method of length in fiberglass reinforced thermoplastic composite |
| CN109666216A (en) * | 2018-12-17 | 2019-04-23 | 会通新材料(上海)有限公司 | A kind of long glass fiber-reinforced polypropylene/polyamide alloy material and preparation method thereof of high-intensitive, low smell |
| CN110818999A (en) * | 2019-09-30 | 2020-02-21 | 广东轻工职业技术学院 | High weld mark strength glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN110818999B (en) * | 2019-09-30 | 2022-11-25 | 广东轻工职业技术学院 | High weld mark strength glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN114507400A (en) * | 2020-10-27 | 2022-05-17 | 合肥杰事杰新材料股份有限公司 | Modified glass fiber reinforced polypropylene composition and preparation method thereof |
| CN114507400B (en) * | 2020-10-27 | 2023-12-08 | 合肥杰事杰新材料股份有限公司 | Modified glass fiber reinforced polypropylene composition and preparation method thereof |
| CN116041841A (en) * | 2022-11-21 | 2023-05-02 | 福建易安特新型建材有限公司 | Glass fiber reinforced modified polypropylene resin and mixing device thereof |
| CN117153470A (en) * | 2023-08-29 | 2023-12-01 | 江苏荣宜电缆有限公司 | Waterproof anti-aging photovoltaic cable and preparation method thereof |
| CN117153470B (en) * | 2023-08-29 | 2024-06-14 | 江苏荣宜电缆有限公司 | Waterproof anti-aging photovoltaic cable and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102731905B (en) | 2014-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102731905B (en) | Long glass fiber reinforced modified polypropylene and preparation method thereof | |
| CN101602884B (en) | Heat-resistant polylactic acid composite material and preparation method thereof | |
| CN102108206B (en) | High-performance nylon resin/calcium sulfate whisker composite material and preparation method thereof | |
| CN101538401A (en) | High temperature resistance binary fiber/polylactic acid based composite material and preparation method thereof | |
| CN107987401A (en) | A kind of heat oxygen aging resistance vegetable fiber reinforced polypropylene composite material and preparation method thereof | |
| CN103102660B (en) | A kind of Fibrilia/polylactic acid biodegradable composite material and preparation method thereof | |
| CN105860316B (en) | Improve the ASA resin composition and preparation method thereof of low-temperature impact toughness | |
| CN105017761A (en) | UV-resistant nylon plastic material | |
| CN106947187A (en) | A kind of sunlight fabric is material modified and preparation method thereof with PVC | |
| CN104045957A (en) | Glass fiber reinforced AES (Acrylonitrile-Ethylene-Propylene-Diene Monomer-Styrene) resin material and preparation method thereof | |
| CN103497490B (en) | A kind of PET composite material and preparation method thereof | |
| CN103849044A (en) | Anti-aging masterbatch used for polyethylene and preparation method of anti-aging masterbatch | |
| CN105462239A (en) | Glass fiber reinforced nylon material for rail and preparation method of glass fiber reinforced nylon material | |
| CN109337192A (en) | A kind of PP composite material and preparation method thereof | |
| CN108219288A (en) | A kind of low-dielectric loss high durable PP composite material and preparation method thereof | |
| CN104277381A (en) | Bamboo fiber-reinforced plastic steel profile for windows and preparation method of bamboo fiber-reinforced plastic steel profile | |
| CN103589053A (en) | Long glass fiber reinforced polypropylene material, and preparation method and application thereof | |
| CN114426760A (en) | Hydrolysis-resistant polyester-based composite material and preparation method thereof | |
| CN108102311A (en) | A kind of low dielectric PBT/PETG alloy nano injection molding composite materials and its preparation method and application | |
| CN109504089B (en) | Low-cost polysulfone alloy | |
| CN102558670A (en) | Flax fiber reinforced polypropylene composite material and its preparation method | |
| CN108396402B (en) | High-toughness polyester staple fiber and preparation method thereof | |
| CN107189214B (en) | A kind of long glass fiber reinforced vehicle material of high infrared reflection and preparation method thereof | |
| CN108250620A (en) | A kind of sol-gel modified braided material of crosslinking | |
| CN109181292A (en) | A kind of glass fiber reinforced PA66 high-speed railway rail baseplate material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Huang Libo Inventor after: Huang Mengbo Inventor before: Huang Libo |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: HUANG LIBO TO: HUANG LIBO HUANG MENGBO |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Huang Longxiang Inventor before: Huang Libo Inventor before: Huang Mengbo |
|
| CB03 | Change of inventor or designer information | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170428 Address after: University of Jinping District 515021 in Guangdong province Shantou City Road Industrial Zone 6-4 downstairs three Patentee after: Guangdong products Plastic Industry Co., Ltd. Address before: Yuyao Zhangting Taiwanese investment zone 315410 in Zhejiang city of Ningbo Province Patentee before: Ningbo Fanlong Plastic New Material Co., Ltd. |
|
| TR01 | Transfer of patent right |