CN102875737A - In-situ remediated and compatibilized polyformaldehyde glass fiber composite composition and preparation thereof - Google Patents
In-situ remediated and compatibilized polyformaldehyde glass fiber composite composition and preparation thereof Download PDFInfo
- Publication number
- CN102875737A CN102875737A CN201210402523XA CN201210402523A CN102875737A CN 102875737 A CN102875737 A CN 102875737A CN 201210402523X A CN201210402523X A CN 201210402523XA CN 201210402523 A CN201210402523 A CN 201210402523A CN 102875737 A CN102875737 A CN 102875737A
- Authority
- CN
- China
- Prior art keywords
- glass fiber
- polyoxymethylene
- volume
- increase
- compound material
- 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
Images
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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- 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
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses in-situ remediated and compatibilized polyformaldehyde glass fiber composite composition and preparation thereof. The composition comprises 60-80 parts of polyformaldehyde, 5-10 parts of carrier resin, 0.01-0.5 part of peroxide initiator, 0.5-2 parts of unsaturated silane coupling agent, 0.5-2 parts of polar-group vinyl monomer, 10-30 parts of glass fiber, 0.1-2 parts of processing aid, 1-3 parts of inorganic filler, and 0.1-0.5 part of anti-oxygen. The preparation includes mixing the components, except for the glass fiber, at high speed, feeding into a twin-screw extruder from a main feed hole, adding the glass fiber from the feed hole, and melting, extruding and granulating. By adding the peroxide initiator, the unsaturated silane coupling agent and the polar-group vinyl monomer as reactive in-situ remediation and compatibilization agents, the glass fiber is remediated in situ by melting and extruding, and the polyformaldehyde/glass fiber composition is compatibilized. The in-situ remediated and compatibilized polyformaldehyde glass fiber composite composition and preparation thereof have the advantages that the preparation is simple and feasible, the composition has excellent compressive properties, and the like.
Description
Technical field
The present invention relates to a kind of macromolecular material mixture, especially relate to a kind of in-situ treatment and increase-volume polyoxymethylene/glass fiber compound material composition and method of making the same.
Background technology
Polyoxymethylene has another name called the polyoxygenated methyne, and molecular structure is regular to make it have good over-all properties and tint permanence with crystallinity, has higher Young's modulus, very high rigidity and hardness, and specific tenacity and specific rigidity are close to metal; Tensile strength, flexural strength, creep resistant and resistance to fatigue are excellent, and anti-repeated stock is unloaded recovery excellent; Frictional coefficient is little, and abrasion performance has the title of metal plastic.Molten polyformaldehyde temperature and decomposition temperature are close, and formability is relatively poor, because polyoxymethylene is crystalline plastic, so molding shrinkage is large, the notched Izod impact strength of material is poor, and breach is relatively more responsive, and thermotolerance, lower temperature resistance are poor.For addressing these problems, usually take to improve die temperature, or carry out anneal, or adding strongthener (such as alkali free glass fibre) carries out modification to polyoxymethylene.
In order to solve the problems referred to above of polyoxymethylene, a lot of patents have been taked the diverse ways modified polyacetal.Find by the retrieval to existing document, patent publication No. is that the Chinese patent of CN 1605456A adopts continuous glass fibre to strengthen polyoxymethylene; Wherein adopted sulfonyl azide class coupling agent, i.e. γ aminopropyltriethoxy silane; The method efficient that this simple Physical is processed glass fibre is not high, because this class coupling agent is present in the system with the form of monomer, very easily vapors away in the course of processing, has reduced service efficiency.Patent publication No. is that the Chinese patent of CN 102417690A has adopted polyurethane to improve the toughness of polyoxymethylene as toughner; But the consistency between this toughner and the polyoxymethylene is relatively poor.Patent publication No. is the Chinese patent of CN101143959, and patent publication No. is that the Chinese patent of CN1421488 all adopts the way that adds compatilizer to improve consistency between the material, is specially and adds the consistency that maleic anhydride grafts is carried polyformaldehyde composite material; Yet the method that adds compatilizer has increased cost and the energy consumption of material.
Summary of the invention
The object of the invention is to overcome the defective that exists in the above-mentioned existing polyformaldehyde composite material preparation process and a kind of in-situ treatment and increase-volume polyoxymethylene/glass fiber compound material composition and method of making the same are provided.
The objective of the invention is to be achieved through the following technical solutions:
The present invention relates to a kind of in-situ treatment and increase-volume polyoxymethylene/glass fiber compound material composition, said composition comprises each component of following parts by weight:
60～80 parts of polyoxymethylene,
5～10 parts of vector resins,
0.01～0.5 part of peroxide initiator,
0.5～2 part of unsaturated silane coupling agent,
0.5～2 part of the vinyl monomer of polar group,
10～30 parts in glass fibre,
0.1～2 part of processing aid,
1～3 part of mineral filler,
0.1～0.5 part in oxidation inhibitor.
Preferably, described polyoxymethylene is one or more the mixture in acefal homopolymer, the copolymerized methanal.More preferably, described polyoxymethylene is the mixture of acefal homopolymer and copolymerized methanal, and wherein, the weight ratio of acefal homopolymer and copolymerized methanal is 20:80～80:20.
Preferably, described vector resin is one or more the mixture in pulverous polyethylene, the polypropylene.
Preferably, described pulverous polyethylene is the linear low density polyethylene powder.Its melt index is 190 ℃ of 1～2g/10min(2.16kg).
Preferably, described peroxide initiator is ditertiary butyl peroxide, dicumyl peroxide, di-isopropylbenzene hydroperoxide, 2,5-dimethyl-2, the mixture of one or more in the 5-two tert-butyl peroxy base hexanes.More preferably, described peroxide initiator is selected dicumyl peroxide, adopts chemical pure product.
Preferably, described unsaturated silane coupling agent is one or more the mixture in vinyltrimethoxy silane, vinyltriethoxysilane, the vinyl front three/Ethoxysilane.More preferably, described unsaturated silane coupling agent is vinyltrimethoxy silane.
Preferably, the vinyl monomer of described polar group is one or more the mixture in maleic anhydride and derivative, fumaric acid anhydride and derivative thereof, the vinyl acetate.More preferably, the vinyl monomer of described polar group is maleic anhydride.
Preferably, described glass fibre is one or several the mixing in alkali-free, chemically-resistant, high-alkali, middle alkali, high strength, high elastic coefficient or the alkali resistant glass fiber, and described glass fibre is continuous glass fibre or staple glass fibre.More preferably, described glass fibre is the alkali-free staple glass fibre.
Preferably, described processing aid is one or more the mixture in polyethylene wax, Poly Propylene Wax, EVA wax, the amide waxe.More preferably, described processing aid is Poly Propylene Wax.
Preferably, described mineral filler is one or more the mixture in calcium carbonate, talcum powder, the wollastonite.More preferably, described mineral filler is 1250 purpose talcum powder.
Preferably, described oxidation inhibitor is one or more the mixture in anti-oxidant DLTP, oxidation inhibitor 246, antioxidant 1076, oxidation inhibitor 1098, antioxidant 1010, irgasfos 168, the antioxidant 330.More preferably, described oxidation inhibitor is irgasfos 168.
The invention still further relates to the preparation method of a kind of aforesaid in-situ treatment and increase-volume polyoxymethylene/glass fiber compound material composition, comprise the steps:
(1) take by weighing by weight each component:
60～80 parts of polyoxymethylene,
5～10 parts of vector resins,
0.01～0.5 part of peroxide initiator,
0.5～2 part of unsaturated silane coupling agent,
0.5～2 part of the vinyl monomer of polar group,
10～30 parts in glass fibre,
0.1～2 part of processing aid,
1～3 part of mineral filler,
0.1～0.5 part in oxidation inhibitor;
(2) above-mentioned each component except glass fibre be placed in the high-speed mixer mix, throw in twin screw extruder, described glass fibre is added by the charging opening by described twin screw extruder, through frit reaction extrude, granulation, and get final product.
Preferably, the screw slenderness ratio of described twin screw extruder is the preferred 44:1 of 40:1～48:1(), be arranged to stepped distribution from described charging opening to the temperature distribution of mouth mould, temperature is controlled between 110～230 degree; It is preferred 2 minutes of 1.5～5min(that the screw speed of described twin screw extruder is controlled at the residence time of described component in described twin screw extruder); The exhaust equipment of described twin screw extruder is arranged at the 4th district to mouthful one or more position (preferably being arranged on the 4th district and Section Eight) in mould district, and the vacuum degree control of described twin screw extruder is at 0.05～0.1Mpa(preferred 0.05～0.08Mpa).
Compared with prior art, the present invention has following beneficial effect:
1, preparation technology of the present invention adopts single stage method to finish, and is simple; Wherein, the generation of processing glass fibre and solubilizing agent is all carried out in polyoxymethylene/glass fiber compound material preparation process; The unsaturated silane coupling agent is under initiator and the strong effect of shearing of screw rod, and " original position " is grafted on vector resin and the polyoxymethylene molecule, and silane group " on the spot " has been finished the process of processing glass fibre in forcing machine; The vinyl monomer of polar group is under peroxide initiator and the strong effect of shearing of screw rod simultaneously, and " original position " is grafted on vector resin and the polyoxymethylene molecule." " improved the consistency between matrix material on the spot.
2, the present invention is by taking the technology of in-situ treatment and increase-volume polyoxymethylene/glass fiber compound material, greatly strengthened the boundary strength of polymeric substrate and glass fibre, make the surface treatment of glass fibre and one step of increase-volume preparation process of system finish the composition excellent combination property.
Description of drawings
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that other features, objects and advantages of the present invention will become:
Fig. 1 is the polyoxymethylene/glass fiber compound material composition SEM photo comparison under 250 multiplying powers of Comparative Examples 2 and embodiment 2; Wherein, a is the SEM photo of Comparative Examples 2, and b is the SEM photo of embodiment 2;
Fig. 2 is the polyoxymethylene/glass fiber compound material composition SEM photo comparison under 500 multiplying powers of Comparative Examples 2 and embodiment 2; Wherein, a is the SEM photo of Comparative Examples 2, and b is the SEM photo of embodiment 2.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.Following examples will help those skilled in the art further to understand the present invention, but not limit in any form the present invention.Should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
In following examples and the Comparative Examples, adopt in the starting material, copolymerized methanal POM M90-44 is the product of Polyplastics Plastics Company, and acefal homopolymer POM 588P is the product of du pont company, and both ratios are 50:50; Linear low density polyethylene 7042 powders are the product of Sinopec Qilu Petrochemical Company, and its melt index is 190 ℃ of 1～2g/10min(2.16kg); The Z-6300 of Dow corning company is vinyltrimethoxy silane; Oxidation inhibitor is the series product of Nanjing Holley bright chemical industry company limited.
Comparative Examples is 1～2
Comparative Examples is that 1～2 component and parts by weight thereof that polyoxymethylene/the glass fiber compound material composition comprises are as shown in table 1; Its preparation method may further comprise the steps:
(1) takes by weighing starting material according to the parts by weight in the form 1;
(2) starting material except glass fibre are mixed in high-speed mixer;
(3) the above-mentioned raw material that mixes is put into twin screw extruder, glass fibre is entered by spout, and the process frit reaction is extruded, granulation.Wherein forcing machine is followed successively by by the temperature design of spout to mouthful mould: 110 ℃, 130 ℃, 150 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, die temperature are 220 ℃.The length-to-diameter ratio of screw rod is 44:1.The screw speed control residence time of material in forcing machine is 2 minutes.Exhaust is arranged on the 4th district and Section Eight, and vacuum tightness is 0.08MPa.
Embodiment 1～4
The in-situ treatment of embodiment 1～4 and component and parts by weight thereof that the increase-volume polyoxymethylene/the glass fiber compound material composition comprises are as shown in table 1; Its preparation method may further comprise the steps:
(1) takes by weighing starting material according to the parts by weight in the form 1;
(2) starting material except glass fibre are mixed in high-speed mixer;
(3) the above-mentioned raw material that mixes is put into twin screw extruder, glass fibre is entered by spout, and the process frit reaction is extruded, granulation.Wherein forcing machine is followed successively by by the temperature design of spout to mouthful mould: 110 ℃, 130 ℃, 150 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, die temperature are 220 ℃.The length-to-diameter ratio of screw rod is 44:1.The screw speed control residence time of material in forcing machine is 2 minutes.Exhaust is arranged on the 4th district and Section Eight, and vacuum tightness is 0.08MPa.
The polyoxymethylene of above-mentioned Comparative Examples 1～2 and embodiment 1～4/glass fiber compound material composition respectively through more than 100 ℃ of vacuum-drying 5h, then according to the ASTM standard, is injection molded into batten test physicals at injection moulding machine; Concrete testing standard is as follows:
Based on the test procedure test tensile property of ASTM D-638,
Based on the test procedure test bending property of ASTM D-790,
Test procedure test I zod notched Izod impact strength based on ASTM D-256.
Test result is as shown in table 2; As shown in Table 2: in-situ treatment of the present invention and increase-volume polyoxymethylene/glass fiber compound material composition have excellent mechanical property, excellent combination property.Respectively the polyoxymethylene of embodiment 2 and Comparative Examples 2/glass fiber compound material composition is adopted the distribution situation of sem test glass fibre, the SEM photo comparison of the two as shown in Figure 1, 2; By Fig. 1,2 as can be known: glass fibre has very good dispersiveness in in-situ treatment of the present invention and the increase-volume polyoxymethylene/glass fiber compound material composition in matrix, glass fibre is uniformly dispersed, and the interface between glass fibre and the base resin is very fuzzy, fiberglass surfacing has obvious base resin to coat, this explanation is through in-situ treatment and In Situ Compatibilization, obviously improve the dispersion of glass fibre in base resin and both bonding forces, thereby improved the macro property of matrix material.
Embodiment 5
The in-situ treatment of embodiment 5 and component and parts by weight thereof that the increase-volume polyoxymethylene/the glass fiber compound material composition comprises are as shown in table 1; Its preparation method is with embodiment 1～4, and institute's difference is:
The screw slenderness ratio of twin screw extruder is 40:1; The screw speed control residence time of material in twin screw extruder is 3 minutes; Exhaust is arranged on Section Eight, and vacuum tightness is 0.05MPa.
Embodiment 6
The in-situ treatment of embodiment 6 and component and parts by weight thereof that the increase-volume polyoxymethylene/the glass fiber compound material composition comprises are as shown in table 1; Its preparation method is with embodiment 1～4, and institute's difference is:
The screw slenderness ratio of twin screw extruder is 48:1; The screw speed control residence time of material in twin screw extruder is 20 minutes; Exhaust is arranged on the 4th district, the 6th district, and vacuum tightness is 0.1MPa.
Table 1
Table 2
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 | Comparative Examples 2 |
| Notch shock (kJ/m 2) | 6.0 | 5.8 | 5.7 | 5.8 | 4.2 | 5.2 |
| Tensile strength (MPa) | 125 | 115 | 128 | 120 | 105 | 110 |
| Modulus in flexure (MPa) | 6100 | 5800 | 6210 | 5780 | 5670 | 6010 |
| Flexural strength (MPa) | 135 | 130 | 138 | 131 | 125 | 130 |
[0072]In sum, preparation technology of the present invention adopts single stage method to finish, and is simple; Wherein, the generation of processing glass fibre and solubilizing agent is all carried out in polyoxymethylene/glass fiber compound material preparation process; The unsaturated silane coupling agent is under initiator and the strong effect of shearing of screw rod, and " original position " is grafted on vector resin and the polyoxymethylene molecule, and silane group " on the spot " has been finished the process of processing glass fibre in forcing machine; The vinyl monomer of polar group is under peroxide initiator and the strong effect of shearing of screw rod simultaneously, and " original position " is grafted on vector resin and the polyoxymethylene molecule." on the spot " improved consistency between matrix material; Simultaneously, the present invention is by taking the technology of in-situ treatment and increase-volume polyoxymethylene/glass fiber compound material, greatly strengthened the boundary strength of polymeric substrate and glass fibre, made the surface treatment of glass fibre and one step of increase-volume preparation process of system finish the composition excellent combination property.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (13)
1. an in-situ treatment and increase-volume polyoxymethylene/glass fiber compound material composition is characterized in that, described composition comprises each component of following parts by weight:
60～80 parts of polyoxymethylene,
5～10 parts of vector resins,
0.01～0.5 part of peroxide initiator,
0.5～2 part of unsaturated silane coupling agent,
0.5～2 part of the vinyl monomer of polar group,
10～30 parts in glass fibre,
0.1～2 part of processing aid,
1～3 part of mineral filler,
0.1～0.5 part in oxidation inhibitor.
2. in-situ treatment as claimed in claim 1 and increase-volume polyoxymethylene/glass fiber compound material composition is characterized in that, described polyoxymethylene is one or more the mixture in acefal homopolymer, the copolymerized methanal.
3. in-situ treatment as claimed in claim 1 and increase-volume polyoxymethylene/glass fiber compound material composition is characterized in that, described vector resin is one or more the mixture in pulverous polyethylene, the polypropylene.
4. in-situ treatment as claimed in claim 3 and increase-volume polyoxymethylene/glass fiber compound material composition is characterized in that, described pulverous polyethylene is the linear low density polyethylene powder.
5. in-situ treatment as claimed in claim 1 and increase-volume polyoxymethylene/glass fiber compound material composition, it is characterized in that, described peroxide initiator is ditertiary butyl peroxide, dicumyl peroxide, di-isopropylbenzene hydroperoxide, 2,5-dimethyl-2, the mixture of one or more in the 5-two tert-butyl peroxy base hexanes.
6. in-situ treatment as claimed in claim 1 and increase-volume polyoxymethylene/glass fiber compound material composition, it is characterized in that, described unsaturated silane coupling agent is one or more the mixture in vinyltrimethoxy silane, vinyltriethoxysilane, the vinyl front three/Ethoxysilane.
7. in-situ treatment as claimed in claim 1 and increase-volume polyoxymethylene/glass fiber compound material composition, it is characterized in that, the vinyl monomer of described polar group is one or more the mixture in maleic anhydride and derivative, fumaric acid anhydride and derivative thereof, the vinyl acetate.
8. in-situ treatment as claimed in claim 1 and increase-volume polyoxymethylene/glass fiber compound material composition, it is characterized in that, described glass fibre is one or several the mixing in alkali-free, chemically-resistant, high-alkali, middle alkali, high strength, high elastic coefficient or the alkali resistant glass fiber, and described glass fibre is continuous glass fibre or staple glass fibre.
9. in-situ treatment as claimed in claim 1 and increase-volume polyoxymethylene/glass fiber compound material composition is characterized in that, described processing aid is one or more the mixture in polyethylene wax, Poly Propylene Wax, EVA wax, the amide waxe.
10. in-situ treatment as claimed in claim 1 and increase-volume polyoxymethylene/glass fiber compound material composition is characterized in that, described mineral filler is one or more the mixture in calcium carbonate, talcum powder, the wollastonite.
11. in-situ treatment as claimed in claim 1 and increase-volume polyoxymethylene/glass fiber compound material composition, it is characterized in that, described oxidation inhibitor is one or more the mixture among anti-oxidant DLTP, oxidation inhibitor 246, antioxidant 1076, oxidation inhibitor 1098, antioxidant 1010, irgasfos 168, antioxidant 330, the oxidation inhibitor PL-34.
12. the preparation method of an in-situ treatment as claimed in claim 1 and increase-volume polyoxymethylene/glass fiber compound material composition is characterized in that, this preparation method may further comprise the steps:
(1) takes by weighing described each component by described weight part;
(2) each component except glass fibre is mixed in high-speed mixer after, throw in twin screw extruder, described glass fibre is added by the charging opening of described twin screw extruder, melting, extrude, granulation, namely get described in-situ treatment and increase-volume polyoxymethylene/glass fiber compound material composition.
13. the preparation method of in-situ treatment as claimed in claim 12 and increase-volume polyoxymethylene/glass fiber compound material composition, it is characterized in that, the screw slenderness ratio of described twin screw extruder is 40:1～48:1, be arranged to stepped distribution from described charging opening to the temperature distribution of mouth mould, temperature is controlled between 110～230 degree; It is 1.5～5min that the screw speed of described twin screw extruder is controlled at the described residence time of each component in described twin screw extruder; The exhaust equipment of described twin screw extruder is arranged at the 4th district to mouthful one or more position in mould district, and the vacuum degree control of described twin screw extruder is at 0.05～0.1MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210402523.XA CN102875737B (en) | 2012-10-19 | 2012-10-19 | In-situ remediated and compatibilized polyformaldehyde glass fiber composite composition and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210402523.XA CN102875737B (en) | 2012-10-19 | 2012-10-19 | In-situ remediated and compatibilized polyformaldehyde glass fiber composite composition and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102875737A true CN102875737A (en) | 2013-01-16 |
| CN102875737B CN102875737B (en) | 2014-12-03 |
Family
ID=47477279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210402523.XA Expired - Fee Related CN102875737B (en) | 2012-10-19 | 2012-10-19 | In-situ remediated and compatibilized polyformaldehyde glass fiber composite composition and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102875737B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724929A (en) * | 2014-01-08 | 2014-04-16 | 四川大学 | High-mechanical-strength polyformaldehyde composite and preparation method thereof |
| CN104177551A (en) * | 2014-08-26 | 2014-12-03 | 太仓碧奇新材料研发有限公司 | Polyoxymethylene homopolymer composite material for 3D printing and preparation method of composite material |
| CN104356312A (en) * | 2014-11-24 | 2015-02-18 | 江苏苏博特新材料股份有限公司 | Grafted polyoxymethylene and preparation method |
| CN110317403A (en) * | 2018-03-30 | 2019-10-11 | 合肥杰事杰新材料股份有限公司 | A kind of modified fibre filled composite materials and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060111507A1 (en) * | 2002-08-19 | 2006-05-25 | Ticona Gmbh | Impact-resistant polyoxymethylene moulding compounds, use thereof and moulding compounds produced therefrom |
| CN101343396A (en) * | 2008-08-18 | 2009-01-14 | 巨石集团有限公司 | Glass fiber reinforced acetal resin composite material |
| CN101665603A (en) * | 2009-09-28 | 2010-03-10 | 四川大学 | PP/PET in-situ microfibrillar reinforcing blend compatibilized by one-step reaction method |
| CN101948606A (en) * | 2010-11-02 | 2011-01-19 | 华东理工大学 | High wear-resistant self-lubrication polyformaldehyde composite material and preparation method thereof |
| CN102076726A (en) * | 2008-07-03 | 2011-05-25 | 陶氏康宁公司 | Polymers modified by silanes |
-
2012
- 2012-10-19 CN CN201210402523.XA patent/CN102875737B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060111507A1 (en) * | 2002-08-19 | 2006-05-25 | Ticona Gmbh | Impact-resistant polyoxymethylene moulding compounds, use thereof and moulding compounds produced therefrom |
| CN102076726A (en) * | 2008-07-03 | 2011-05-25 | 陶氏康宁公司 | Polymers modified by silanes |
| CN101343396A (en) * | 2008-08-18 | 2009-01-14 | 巨石集团有限公司 | Glass fiber reinforced acetal resin composite material |
| CN101665603A (en) * | 2009-09-28 | 2010-03-10 | 四川大学 | PP/PET in-situ microfibrillar reinforcing blend compatibilized by one-step reaction method |
| CN101948606A (en) * | 2010-11-02 | 2011-01-19 | 华东理工大学 | High wear-resistant self-lubrication polyformaldehyde composite material and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724929A (en) * | 2014-01-08 | 2014-04-16 | 四川大学 | High-mechanical-strength polyformaldehyde composite and preparation method thereof |
| CN103724929B (en) * | 2014-01-08 | 2016-02-03 | 四川大学 | A kind of High-mechanical-strepolyformaldehyde polyformaldehyde composite and preparation method thereof |
| CN104177551A (en) * | 2014-08-26 | 2014-12-03 | 太仓碧奇新材料研发有限公司 | Polyoxymethylene homopolymer composite material for 3D printing and preparation method of composite material |
| CN104177551B (en) * | 2014-08-26 | 2016-09-14 | 太仓碧奇新材料研发有限公司 | 3D prints with acefal homopolymer composite and preparation method thereof |
| CN104356312A (en) * | 2014-11-24 | 2015-02-18 | 江苏苏博特新材料股份有限公司 | Grafted polyoxymethylene and preparation method |
| CN110317403A (en) * | 2018-03-30 | 2019-10-11 | 合肥杰事杰新材料股份有限公司 | A kind of modified fibre filled composite materials and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102875737B (en) | 2014-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101787204B (en) | Low water absorption polyamide composite and preparation method thereof | |
| CN101544821B (en) | High performance nylon composite for railway fastener gauge apron and its preparation method | |
| CN103382296B (en) | A kind of poly butylene succinate resin combination and preparation method thereof | |
| CN102875737B (en) | In-situ remediated and compatibilized polyformaldehyde glass fiber composite composition and preparation thereof | |
| CN101747600B (en) | Method for preparing polyethylene terephthalate (PET) blend | |
| CN101875790B (en) | Preparation method of surface hydrolysis modified aramid fiber enhanced wood plastic composite material | |
| CN103030884B (en) | Polypropylene composition for automobile enamel-plastic instrument panel frameworks and preparation method thereof | |
| CN107709445B (en) | Fiber reinforced polypropylene composition with high strain at break | |
| CN109456563B (en) | Special material for UHMWPE alloy compatibilization toughening modified polypropylene corrugated pipe and preparation method thereof | |
| CN101870811A (en) | Cold-resistance super tough nylon polyolefin alloy and preparation method thereof | |
| CN101314660A (en) | Method for preparing high impact modified material with waste and old polystyrene plastics | |
| CN103554869B (en) | Polycarbonate composite material that a kind of polyolefin elastomer is toughness reinforcing and preparation method thereof | |
| CN102643484A (en) | In-situ compatibilization polyolefin/polystyrene alloy and preparation method and application thereof | |
| CN102002233B (en) | Mixture for preparing nylon nano composite material and preparation method of composite material | |
| CN110862618A (en) | Ultra-low-warpage high-strength long glass fiber reinforced polypropylene composite material and preparation method thereof | |
| CN111234341A (en) | Special high-strength high-toughness HDPE (high-density polyethylene) glass fiber master batch for large-diameter pipes and preparation method thereof | |
| CN101735398A (en) | Interfacial compatilizer for wood-plastic composite material and method for preparing same | |
| CN109081894B (en) | High-fluidity toughening agent and preparation method thereof | |
| CN1126784C (en) | Glass-fibre reinforced warp-resistant polypropylene with low shrinkage ratio | |
| CN108059771A (en) | One kind has high melt strength, propylene micro-foaming material and preparation method thereof | |
| CN102153830B (en) | ACS (acrylonitrile-chlorinated polyethylene-styrene) resin composition and method for preparing same | |
| CN1858113A (en) | Tenacity reinforced nylon and its preparing method | |
| CN114231046B (en) | High-strength high-heat-resistance wood-plastic composite material and preparation method thereof | |
| CN113388192B (en) | High-toughness low-temperature-resistant high-gloss regenerated PP modified material and preparation method thereof | |
| CN110066463B (en) | Self-reaction toughened polypropylene composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170505 Address after: 200000 Shanghai city Pudong New Area Jing Road No. 351 Building No. 2 room A685-03 Co-patentee after: Shanghai Niuk New Plastic Technology Co., Ltd. Patentee after: Shanghai New York Polytron Technologies Inc Address before: 201700, No. 2, No. 99, Lane 99, Huafang Road, Qingpu District, Shanghai Patentee before: Shanghai Niuk New Plastic Technology Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141203 Termination date: 20181019 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |