CN102690482B - Oil-containing poly-dicyclopentadiene composite material and preparation method thereof - Google Patents
Oil-containing poly-dicyclopentadiene composite material and preparation method thereof Download PDFInfo
- Publication number
- CN102690482B CN102690482B CN201110382463.5A CN201110382463A CN102690482B CN 102690482 B CN102690482 B CN 102690482B CN 201110382463 A CN201110382463 A CN 201110382463A CN 102690482 B CN102690482 B CN 102690482B
- Authority
- CN
- China
- Prior art keywords
- dicyclopentadiene
- composite material
- oil
- preparation
- lubricating oil
- 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.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an oil-containing poly-dicyclopentadiene composite material and a preparation method thereof. The poly-dicyclopentadiene composite material is mainly prepared by catalytically blending and polymerizing the following raw materials in parts by weight: 70-95 parts of dicyclopentadiene and 5-30 parts of lubricating oil. The lubricating oil is paraffin oil, silicone oil or heavy liquid paraffin. The lubricating oil is blended with the poly-dicyclopentadiene to obtain the poly-dicyclopentadiene composite material, so the wear resistance of the composite material under dry friction conditions is obviously enhanced, the antiwear performance is 2-3 times higher than that in the prior art, and the high holding modulus and high shock strength of the composite material are maintained; and thus, the composite material can be used for preparing parts having wider application range.
Description
Technical field
The present invention relates to a kind of oil-containing Polydicyclopentadiencomposite composite material, relate to the preparation method of this matrix material simultaneously, belong to technical field of polymer materials.
Background technology
Polydicyclopentadiene (Polydicyclopentadiene, english abbreviation PDCPD) be a kind of engineering plastics that have impact and high-modulus concurrently that are polymerized by monomer dicyclopentadiene under the effect of catalyzer, monomer whose dicyclopentadiene is the larger a kind of byproduct of output in petrochemical complex ethylene production.The material of the characteristics such as the thermotolerance that polydicyclopentadiene engineering plastics have had, creep resistance, dimensional stability, shape memory, erosion resistance, lightweight, can be used for manufacturing various high-performance, high added value, high-grade fine product.As: the bumper in transportation, backplate, side plate, engine shield and bodyshell etc.; The housing of the large electric equipment such as the electric motor in electric installation, air conditioning machinery; The member of the snowmobile in sports equipment, surfboard, golf cart etc. and agricultural machine, civil construction material etc.The states such as the U.S., Japan, Europe have realized the industrial production of polydicyclopentadiene, and China does not also have polydicyclopentadiene production technology and the material of the domestic trade mark so far.
External existing polydicyclopentadiene is produced and is adopted reaction injection moulding (RIM, Reaction Injection Molding) and resin transfer molding (RTM, Resin Transfer Molding) technique, these two kinds of techniques all have the superior features such as shaping speed is fast, processing temperature is low, injection pressure is low.The catalyst system using at present comprises the carbone catalyst of aryloxy tungsten complex, molybdenum, ruthenium and osmium.Wherein aryloxy tungsten complex catalyzer must have promotor could effectively make dicyclopentadiene generation polymerization, belongs to two-pack coordination catalyst system.Because its cost is lower, be use at present more a kind of.
Chinese patent CN1084340C discloses a kind of method that adopts double-metal composite catalyst and the compound aluminum alkyls zinc of promotor halogenide to prepare polydicyclopentadiene, and products obtained therefrom has the advantages such as high-impact, high modulus in flexure.Chinese patent CN101205344A discloses the carrier loaded tungsten owner of nano imvite catalyzer makes dicyclopentadiene polymerization prepare the method for dicyclopentadiene material under the acting in conjunction of promotor aluminum alkyls.Chinese patent CN101597351A discloses the preparation method of a class polydicyclopentadiene/rubber composite, and resulting materials has good shock resistance.Chinese patent CN101987907A discloses a kind of Polydicyclopentadiencomposite composite material, and by adding inorganic nano-filler and polymer particles, gained matrix material, when improving modulus and resistance to impact shock, has good water-fast slurry wear performance.But the wear resisting property of the Polydicyclopentadiencomposite composite material obtaining by aforesaid method under DRY SLIDING is poor, can not meet the demand in market, limited it and applied.
Summary of the invention
The object of this invention is to provide the good Polydicyclopentadiencomposite composite material of wear resistance under a kind of DRY SLIDING, there is higher tensile strength, resistance to impact shock simultaneously.
In order to realize above object, the technical scheme that Polydicyclopentadiencomposite composite material of the present invention adopts is: a kind of oil-containing Polydicyclopentadiencomposite composite material, mainly that catalytic material blending polymerization by following weight part forms: dicyclopentadiene 70-95 part, lubricating oil 5-30 part; Described lubricating oil is paraffin oil, silicone oil or heavy liquid paraffin.
Oil-containing polydicyclopentadiene of the present invention is adopted with the following method and is made:
Its step is as follows:
1) dicyclopentadiene and the lubricating oil of getting formula ratio mix, and stir and obtain dicyclopentadiene dispersion liquid;
2) dicyclopentadiene dispersion liquid is divided into A, B two portions, in A part, adds the Primary Catalysts of dicyclopentadiene molar weight 0.001～0.003, in B part, add Primary Catalysts mole number 5-20 promotor doubly;
3), under 40-60 ℃ of condition, A part and the moulding of B part in-situ polymerization blending are obtained to Polydicyclopentadiencomposite composite material.
Step 3) after described in-situ polymerization blending moulding, under protection of inert gas in 80-200 ℃ of heating 40-80 minute.
Described Primary Catalysts is aryloxy tungsten catalyst, has following general formula:
1. [(ArO)
nwC1
6-n], n=1,2,3 or 4 wherein; Or
2. [(ArO)
nwOC1
4-n], n=1 to 2 wherein;
In two general formulas, ArO is many alkyl substituted benzenes oxygen base, and its general structure is:
R wherein
1, R
2, R
3can be hydrogen atom, or carbonatoms be C
1-10straight chained alkyl or branched-chain alkyl.
Described promotor is tin alkyl, and its general structure is H
xsnR
4-x, wherein R is that carbonatoms is C
1-10straight chained alkyl or branched-chain alkyl or phenyl, substituted-phenyl; X is 0 or 1.
The present invention's Polydicyclopentadiencomposite composite material that blend lubricating oil is prepared in polydicyclopentadiene, significantly improved the wear resisting property of matrix material under DRY SLIDING, its wear resistance exceeds 2-3 doubly than prior art, keep maintenance modulus and shock strength that matrix material is higher simultaneously, thereby can prepare the product that range of application is wider with this matrix material.
Embodiment
Embodiment 1
The Polydicyclopentadiencomposite composite material of the present embodiment is that the catalytic material blending polymerization by following weight part forms: 95 parts of dicyclopentadiene, 5 parts of paraffin oil (Chengdu Gracia chemical technology company limiteds, CP), all the other are residual catalyzer and inevitable impurity.
The preparation method of the Polydicyclopentadiencomposite composite material of the present embodiment is as follows:
1) under 50 ℃ of conditions, 5 parts of paraffin oils are added on to purity to be greater than in 95 parts of dicyclopentadiene of 98%, after stirring, make dicyclopentadiene-paraffin oil dispersion, and obtained dicyclopentadiene dispersion is carried out after degassed to blanketing with inert gas is stand-by again;
2) under nitrogen protection respectively to the dicyclopentadiene-paraffin oil dispersion (amounting to 40 kilograms, containing 2 kilograms of paraffin oils) that adds 20 kilograms in the A batch can of reaction injection molding machine and B batch can, whole system sealing and blanketing with inert gas; In A batch can, add 0.119 kilogram three [2,6-di-isopropyl phenoxy group] tungsten trichloride catalyzer (for add dicyclopentadiene mole number 1/2000), in B batch can, add 0.418 kilogram of tri-butyl tin hydride (be in A batch can tungsten catalyst mole number 10 times);
3) temperature of the material A in reaction injection molding machine A, B tank and material B is remained on to 50 ℃; the material pump of simultaneously opening two reaction injection molding machines carries out material stirring and circulation; make material A and the further homogenize of material B; by injection head dock with die orifice; open filling gun, material A and material B inject mould simultaneously, die sinking in 20 minutes; obtain Polydicyclopentadiencomposite composite material, matrix material is heated 80 minutes in 80 ℃ under protection of inert gas.
Embodiment 2
The Polydicyclopentadiencomposite composite material of the present embodiment is that the catalytic material blending polymerization by following weight part forms: 85 parts of dicyclopentadiene, 15 parts of silicone oil, all the other are residual catalyzer and inevitable impurity.
The preparation method of the Polydicyclopentadiencomposite composite material of the present embodiment is as follows:
1) under 60 ℃ of conditions, 15 parts of silicone oil are added on to purity and are greater than in 85 parts of dicyclopentadiene of 98%, after stirring, make dicyclopentadiene-silicone oil dispersion, and obtained dicyclopentadiene dispersion is carried out after degassed to blanketing with inert gas is stand-by again;
2) under nitrogen protection respectively to the dicyclopentadiene-silicone oil dispersion (amounting to 40 kilograms, 6 kilograms of silicate-containing oils) that adds 20 kilograms in the A batch can of resin transfer molding machine and B batch can, whole system sealing and blanketing with inert gas; In A batch can, add 0.212 kilogram three [2,6-di-isopropyl phenoxy group] tungsten trichloride catalyzer (for add dicyclopentadiene mole number 1/1000), in B batch can, add 0.749 kilogram of tri-butyl tin hydride (be in A batch can tungsten catalyst mole number 20 times);
3) temperature of the material A in resin transfer molding machine A, B tank and material B is remained on to 60 ℃; the material pump of simultaneously opening two resin transfer molding machines carries out material stirring and circulation; make material A and the further homogenize of material B; by injection head dock with die orifice; open filling gun, material A and material B inject mould simultaneously, die sinking in 20 minutes; obtain Polydicyclopentadiencomposite composite material, matrix material is heated 60 minutes in 140 ℃ under protection of inert gas.
Embodiment 3
The Polydicyclopentadiencomposite composite material of the present embodiment is that the catalytic material blending polymerization by following weight part forms: 70 parts of dicyclopentadiene, 30 parts of heavy liquid paraffin (Aladdin reagent company), all the other are residual catalyzer and inevitable impurity.
The preparation method of the Polydicyclopentadiencomposite composite material of the present embodiment is as follows:
1) under 40 ℃ of conditions, 30 parts of heavy liquid paraffin are added on to purity to be greater than in 70 parts of dicyclopentadiene of 98%, after stirring, make dicyclopentadiene-heavy liquid paraffin dispersion, and obtained dicyclopentadiene dispersion is carried out after degassed to blanketing with inert gas is stand-by again;
2) under nitrogen protection, in the A batch can of reaction injection molding machine and B batch can, add dicyclopentadiene-heavy liquid paraffin dispersion of 20 kilograms (to amount to 40 kilograms respectively, containing 12 kilograms, heavy liquid paraffin), whole system sealing and blanketing with inert gas; In A batch can, add 0.058 kilogram three [2,6-di-isopropyl phenoxy group] tungsten trichloride catalyzer (for add dicyclopentadiene mole number 1/3000), in B batch can, add 0.308 kilogram of tri-butyl tin hydride (be in A batch can tungsten catalyst mole number 10 times);
3) temperature of the material A in reaction injection molding machine A, B tank and material B is remained on to 40 ℃; the material pump of simultaneously opening two reaction injection molding machines carries out material stirring and circulation; make material A and the further homogenize of material B; by injection head dock with die orifice; open filling gun, material A and material B inject mould simultaneously, die sinking in 20 minutes; obtain Polydicyclopentadiencomposite composite material, matrix material is heated 40 minutes in 200 ℃ under protection of inert gas.
Be necessary to be pointed out that at this, above embodiment and comparative example are only used to further illustrate the present invention, and can not be interpreted as limiting the scope of the invention; Catalyzer of the present invention, wherein the phenoxy group of Primary Catalysts replaces the integer that number can adopt 1-4, and the substituting group on phenoxy group substituting group can adopt the alkyl substituent of hydrogen or 1-10 carbon; Wherein the replacement number of the alkyl substituent of promotor can be 3 or 4, and substituting group can adopt the alkyl substituent of 1-4, above this for those skilled in the art be equal to replacement means, should fall into protection scope of the present invention.
Comparative example 1
This comparative example provides a kind of polydicyclopentadiene/ultrahigh molecular weight polyethylene(UHMWPE)/expansion nano graphite composite material as contrast of the present invention, and its preparation method is as follows:
1) expansible black lead is expanded under 950 ℃ of high temperature 15-30s makes expanded graphite, after the expanded graphite making is dispersed in and in 70% ethanol, carries out the ultrasonic mechanical stirring that adds and pulverize, suction filtration is dried and is made the expansion nano graphite granule that particle diameter is less;
2) weigh 0.20 kilogram of above-mentioned expanded graphite, join in 1000mL dry toluene, after ultrasonic dispersion 30min, add 8g tolylene diisocyanate (TDI), at room temperature react after 1h, filter and use petroleum ether to remove unreacted TDI, vacuum drying is to constant weight, react 6h with 5-norbornylene-2-methyl alcohol 4g again, use DMSO washing, vacuum-drying 12h obtains black powder, obtains modified expanded graphite;
3) under 50 ℃ of conditions, the ultrahigh molecular weight polyethylene(UHMWPE) that is 3% by mass percent is scattered in purity and is greater than in 98% dicyclopentadiene, after stirring, make dicyclopentadiene-ultrahigh molecular weight polyethylene(UHMWPE) dispersion liquid, the modified expanded nano-graphite that is 0.5% by mass percent is added into above-mentioned system, stir, form dicyclopentadiene-ultrahigh molecular weight polyethylene(UHMWPE)-modified nano graphite dispersion liquid and obtained dispersion liquid is carried out after degassed to blanketing with inert gas is stand-by again;
4) under nitrogen protection respectively to the dicyclopentadiene styrene-butadiene rubber(SBR) solution (amounting to 40 kilograms, containing 12 kilograms of ultrahigh molecular weight polyethylene(UHMWPE)s, 02 kilogram of modified nano graphite) that adds 20 kilograms in the A batch can of reaction injection molding machine and B batch can.Whole system sealing and blanketing with inert gas.
Three [2,6-di-isopropyl phenoxy group] the tungsten trichloride catalyzer that adds 0.124 kilogram in A batch can is 1/2000 of two portions dicyclopentadiene total mole number.
In B batch can, adding 0.881 kilogram of tri-butyl tin hydride, is 20 times of tungsten catalyst mole number in A batch can.
5) temperature of the polymer material A in resin transfer molding machine A, B tank and polymer material B is remained on to 50 ℃, the material pump of simultaneously opening resin transfer molding machine carries out material stirring and circulation, makes material A and the further homogenize of material B.The injection head of resin transfer molding machine is docked with die orifice, open filling gun, material A and material B inject mould simultaneously, and die sinking in 20 minutes obtains polydicyclopentadiene/ultrahigh molecular weight polyethylene(UHMWPE)/expansion nano graphite composite material.
Comparative example 2
This comparative example provides a kind of polydicyclopentadiene/nano calcium carbonate composite material as contrast of the present invention, and its preparation method is as follows:
1) accurately weigh 0.04 kilogram of nano-calcium carbonate, join in the butanols aqueous solution (40%) of 120mL, after ultrasonic dispersion 30min, add 2g sodium stearate, at 80 ℃, react after 2h, vacuum drying, makes modified nano calcium carbonate;
2) under 10 ℃ of conditions of 50 scholar, the modified nano calcium carbonate that is 0.1% by mass percent joins purity and is greater than in 98% dicyclopentadiene, stir, form dicyclopentadiene-nano-calcium carbonate dispersion liquid, and obtained dispersion liquid is carried out after degassed using nitrogen protection stand-by again;
3) under nitrogen protection respectively to the dicyclopentadiene-nano-calcium carbonate dispersion liquid (amounting to 40 kilograms, containing 40 grams of modified nano calcium carbonates) that adds 20 kilograms in the A batch can of reaction injection molding machine and B batch can.Whole system seals and protects with nitrogen gas;
Three [2,6-di-isopropyl phenoxy group] the tungsten trichloride catalyzer that adds 0.124 kilogram in A batch can is 1/2000 of two portions dicyclopentadiene total mole number.
In B batch can, adding 0.880 kilogram of tri-butyl tin hydride, is 20 times of tungsten catalyst mole number in A batch can.
4) temperature of the material A in reaction injection molding machine A, B tank and material B is remained on to 10 ℃ of 50 scholars, the material pump of simultaneously opening two reaction injection molding machines stirs and circulates, make material A and the further homogenize of material B, the injection head of reaction injection molding machine is docked with die orifice, open filling gun, material A and material B inject mould in filling gun after high-speed mixing, die sinking in 20 minutes, obtains polydicyclopentadiene/nano calcium carbonate composite material.
Test
The mensuration of embodiment 1-3 and comparative example 1-2 being carried out respectively to tensile strength, resistance to impact shock, frictional coefficient and quality wear rate, the result of its mensuration is as shown in table 1:
The performance measurement result of table 1 embodiment and comparative example matrix material
| Test event | Example 1 | Example 2 | Example 3 | Contrast 1 | Contrast 2 |
| Tensile strength (MPa) | 29 | 28 | 28 | 28 | 29 |
| Resistance to impact shock (J/m) | 95 | 99 | 98 | 92 | 90 |
| Frictional coefficient | 0.55 | 0.52 | 0.45 | 0.72 | 0.71 |
| Quality wear rate (10 -6g·m -1) | 5.8 | 5.2 | 4.1 | 11.3 | 12.9 |
As can be seen from Table 1, compared with prior art, in polydicyclopentadiene, add after lubricating oil, when keeping its tensile strength and resistance to impact shock, can reduce its frictional coefficient, and obviously reduce its quality wear rate, the 31.8%-46% that quality wear rate is prior art.
Claims (4)
1. a preparation method for oil-containing Polydicyclopentadiencomposite composite material, is characterized in that: described oil-containing Polydicyclopentadiencomposite composite material is mainly that the catalytic material blending polymerization by following weight part forms: dicyclopentadiene 70-95 part, lubricating oil 5-30 part; Described lubricating oil is paraffin oil, silicone oil or heavy liquid paraffin; The step of its preparation method is as follows:
1) dicyclopentadiene and the lubricating oil of getting formula ratio mix, and stir and obtain dicyclopentadiene dispersion liquid;
2) dicyclopentadiene dispersion liquid is divided into A, B two portions, in A part, adds the Primary Catalysts of dicyclopentadiene molar weight 0.001～0.003, in B part, add Primary Catalysts mole number 5-20 promotor doubly;
3), under 40-60 ℃ of condition, A part and the moulding of B part in-situ polymerization blending are obtained to Polydicyclopentadiencomposite composite material.
2. preparation method according to claim 1, is characterized in that: described in step 3), after in-situ polymerization blending moulding, under protection of inert gas, in 80-200 ℃, heat 40-80 minute.
3. preparation method according to claim 1, is characterized in that: described Primary Catalysts is aryloxy tungsten catalyst, has following general formula:
1. [(ArO)
nwC1
6-n], n=l, 2,3 or 4 wherein; Or
2. [(ArO)
nwOC1
4-n], n=l to 2 wherein; In two general formulas, ArO is many alkyl substituted benzenes oxygen base, and its general structure is:
R1 wherein, R2, R3 can be hydrogen atom, or carbonatoms is C
1-10straight chained alkyl or branched-chain alkyl.
4. preparation method according to claim 1, is characterized in that: described promotor is tin alkyl, and its general structure is H
xsnR
4-x, wherein R is that carbonatoms is C
1-10straight chained alkyl or branched-chain alkyl or phenyl, substituted-phenyl; X is 0 or 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110382463.5A CN102690482B (en) | 2011-11-25 | 2011-11-25 | Oil-containing poly-dicyclopentadiene composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110382463.5A CN102690482B (en) | 2011-11-25 | 2011-11-25 | Oil-containing poly-dicyclopentadiene composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102690482A CN102690482A (en) | 2012-09-26 |
| CN102690482B true CN102690482B (en) | 2014-07-16 |
Family
ID=46856229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110382463.5A Expired - Fee Related CN102690482B (en) | 2011-11-25 | 2011-11-25 | Oil-containing poly-dicyclopentadiene composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102690482B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106398075A (en) * | 2016-08-31 | 2017-02-15 | 湖南华强电气股份有限公司 | DCPD composite material for vehicle air-conditioner base |
| CN106479102A (en) * | 2016-08-31 | 2017-03-08 | 湖南华强电气股份有限公司 | Car air-conditioner DCPD composite cover plate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597351A (en) * | 2009-06-25 | 2009-12-09 | 河南科技大学 | The polydicyclopentadien//rubber in-situ polymerization blending composite material preparation method |
| CN102199252A (en) * | 2011-03-30 | 2011-09-28 | 黎明化工研究院 | Flame-retardant polydicyclopentadiene composition, and thermosetting material and preparation method thereof |
-
2011
- 2011-11-25 CN CN201110382463.5A patent/CN102690482B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597351A (en) * | 2009-06-25 | 2009-12-09 | 河南科技大学 | The polydicyclopentadien//rubber in-situ polymerization blending composite material preparation method |
| CN102199252A (en) * | 2011-03-30 | 2011-09-28 | 黎明化工研究院 | Flame-retardant polydicyclopentadiene composition, and thermosetting material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 聚双环戊二烯/无机纳米粒子复合材料的制备与性能;郭永克;《硕士学位论文》;20110913;参见第22页 * |
| 郭永克.聚双环戊二烯/无机纳米粒子复合材料的制备与性能.《硕士学位论文》.2011, |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102690482A (en) | 2012-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101987907B (en) | Polydicyclopentadiene composite material and preparation method thereof | |
| CN101597351B (en) | Preparation method of polydicyclopentadiene/rubber in-situ polymerization blending composite material | |
| CN102942694B (en) | Oil-filled monomer casting nylon composite material | |
| CN105906748B (en) | Functional polyvinyl resin with super-high molecular weight preparation method | |
| KR20200024837A (en) | Polysaccharide-Elastomer Masterbatch Composition | |
| CN109486142B (en) | Polylactic acid-polycaprolactone composite material for 3D printing and preparation method thereof | |
| CN106317273B (en) | Super high molecular weight micronized polyethylene powder and preparation method thereof | |
| CN102690482B (en) | Oil-containing poly-dicyclopentadiene composite material and preparation method thereof | |
| CN106751906B (en) | Preparation method with controllable multiple dimensioned pore structure silicon rubber foam | |
| Wang et al. | Enhanced flame retardancy of natural rubber composite with addition of microencapsulated ammonium polyphosphate and MCM-41 fillers | |
| CN101245116A (en) | Catalytic system for producing ultrahigh molecular weight polyethylene | |
| Cong et al. | Facile preparation of Cross-linked polyester composite rubber with excellent mechanical strength and high toughness by loading adjustable Low-cost clay | |
| CN106928382B (en) | A kind of preparation method of extra high-molecular polythene catalyst | |
| CN108586640A (en) | It is used to prepare the catalyst precarsor and catalyst of ultra-fine ultra-high molecular weight polyethylene | |
| CN111995861A (en) | GO/TPU composite powder for selective laser sintering of heat-resistant workpieces and preparation method thereof | |
| CN110540710A (en) | Thermal-aging-resistant polypropylene nano composite material and preparation method thereof | |
| CN111748188A (en) | Ultrahigh-conductivity nano carbon master batch and preparation method and application thereof | |
| CN114149523B (en) | Catalyst spherical carrier for olefin polymerization, preparation method and application thereof, and catalyst and application thereof | |
| CN109354865A (en) | A kind of high fire-retardance high abrasion plastic pellet and preparation method thereof | |
| CN114437447A (en) | Degradable composite foam material with high mechanical property and preparation method thereof | |
| CN111592606B (en) | Polyethylene powder and preparation method thereof | |
| CN106751320A (en) | A kind of Polydicyclopentadiencomposite composite material and preparation method thereof | |
| CN110643086B (en) | High-elasticity rubber and processing method thereof | |
| CN111518324B (en) | Environment-friendly oil-extended styrene-butadiene rubber and preparation method thereof | |
| CN107698968B (en) | Modified nano particle/oil-containing cast nylon 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140716 Termination date: 20161125 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |