CN104974418A - Polyropylene composite material and preparation method thereof - Google Patents
Polyropylene composite material and preparation method thereof Download PDFInfo
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- CN104974418A CN104974418A CN201410149165.5A CN201410149165A CN104974418A CN 104974418 A CN104974418 A CN 104974418A CN 201410149165 A CN201410149165 A CN 201410149165A CN 104974418 A CN104974418 A CN 104974418A
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- polypropylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
Abstract
The invention discloses a polypropylene composite material and a preparation method thereof, wherein the material includes, by weight, (a) 40-85% of polypropylene resin, (b) 5-30% of a toughening agent, (c) 5-40% of a filling material, (d) 0.1-1% of a composite antioxidant, and (e) 0.1-1% of a processing aid. The preparation method includes the steps of (1) weighing the material according to the weight ratio of 40-85% of the polypropylene resin, 5-30% of the toughening agent, 5-40% of the inorganic material, 0.1-1% of the composite antioxidant, and 0.1-1% of the processing aid; (2) mixing the raw materials in a high-speed mixer uniformly; and (3) performing extrusion in a double-screw extruder to obtain a blended substance. The polypropylene composite material is excellent in anti-impact performance, is high in toughness at normal and low temperatures, is excellent in notch impact strength and is excellent in heat resistance and rigidity.
Description
Technical field
The present invention relates to a kind of polypropylene composite material and preparation method thereof.
Background technology
Polyacrylic wide material sources, its relative density is little, and processing characteristics is excellent, and polyacrylic good heat resistance, and its fusing point reaches 164 DEG C, can under 100 ~ 120 DEG C of conditions life-time service.In addition polypropylene also has excellent chemical resistance, electrical insulating property and less dielectric constant, has outstanding rigidity and folding resistance, and its goods are nonpoisonous and tasteless, glossiness good.Thus polypropylene is widely used in the fields such as automobile, machinery, household electrical appliances, packaging.
Although polypropylene has more excellent performance, still there is many weak points when being used as structured material in polypropylene.Polypropylene poor toughness, wear resistance are not enough, molding shrinkage large, low temperature time fragility large, thus limit and expand polyacrylic Application Areas further.
For the shortcoming of the low temperature brittleness deficiency of polypropylene material, there is the achievement in research of a lot of relevant polypropylene toughening both at home and abroad, sum up, mainly chemically with physics two kinds of approach, toughening modifying is carried out to polypropylene.The toughness reinforcing mainly chemical copolymerization method of chemical method, adopts special polymerization technique, other groups on grafting or block on polypropylene segment, thus reduces polyacrylic crystallization, realizes the object that polypropylene toughness improves.
Physics is toughness reinforcing, is the method adopting physical blending, adds rubber, thermoplastic elastomer, rigid particles, nanoparticle etc., realize toughness reinforcing effect in polypropylene.
The mechanism of elastic body toughening PP: on the one hand, elastomerics toughness higher than matrix PP, when elastomerics as dispersed phase distribution in PP external phase, " sea-island " structure can be formed, when blend is subject to External Force Acting, elastomer particle, as focal point of stress, preferentially deforms under external force shock action.If two-phase interface bonding is good, the region at particle place can be made to produce a large amount of crazing and shear zone, thus consume impact energy, elastomer particles also can block, turns to and stop crackle development simultaneously, and the toughness of system is increased; On the other hand, elastomericly add the crystallization destroying PP, make the spherocrystal of PP by refinement, and elastomerics plays the effect of heterogeneous nucleation thus plays toughening effect.But while adopting elastic body toughening that the shock strength of material, elongation at break can be made to increase, the rigidity of material, use temperature and processing characteristics but significantly reduce.
Organic rigid-particle is endergonic by the yield deformation process of self to plastic toughening effect.And inorganic rigid particle, if particle is combined with resin matrix closely, also tensile stress can be born, it can produce stress concentration effect, the easy matrix resin around that causes produces microscopic damage, absorb certain deformation work, and particle can stop crackle to spread or passivation and stop that crackle is unlikely develops into destructive crack.But rigid particles is not obvious to polyacrylic toughening effect, this method needs the problem solved to be the interface cohesion effect of particle and matrix, and rigid particles in the base dispersed, and minimizing is assembled mutually.
Many researchers all selects the mode adopting elastomerics, rigid particles and polypropylene ternary system blended.Adopt elastomerics and rigid particles jointly to carry out toughening modifying to PP, single system mobility caused by elastic body toughening both can have been avoided to decline, single defect of not easily being disperseed in matrix resin by the toughness reinforcing caused nanoparticle of nanoparticle can be solved again.
Summary of the invention
The object of the invention is to provide a kind of polypropylene composite material with excellent shock proof performance.
It is low that further aim of the present invention is to provide a kind of cost, the preparation method of the simple polypropylene composite material of manufacturing process.
Specifically, the present invention relates to the content of following aspect: polypropylene composite material, its integral part is as follows:
(a), acrylic resin 40 ~ 85wt%;
(b), toughner 5 ~ 30wt%;
(c), packing material: 5 ~ 40wt%;
(d), composite antioxidant 0.1 ~ 1wt%;
(e), processing aid 0.1 ~ 1wt%;
Above-mentioned (a) acrylic resin is homo-polypropylene;
Above-mentioned (b) toughner selects the composition of ethylene-octene copolymer (POE), polyurethane elastomer, polystyrene elastomers, terpolymer EP rubber wherein one or more.
Above-mentioned (c) packing material selects the one or more combination thing of talcum powder, calcium carbonate, barium sulfate, kaolin, wollastonite, polynite, calcium carbonate crystal whisker composition.
The one or more combination thing that above-mentioned (d) composite antioxidant selects Hinered phenols antioxidant, phosphite antioxidant, sulfur-bearing oxidation inhibitor to form.As four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid positive octadecanol ester, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, two (2,4-DTBP) pentaerythritol diphosphites, two (18) ester of thio-2 acid, the hard alcohol ester composition of thio-2 acid two one or more combination thing.
Above-mentioned (e) processing aid selects the one of calcium stearate, ethylene hard acid acyl amine (EBS), or two kinds of mixtures.
A kind of polypropylene composite material for the preparation of having excellent shock proof performance, material is weighed: acrylic resin 40 ~ 85% by following weight proportion, toughner 5 ~ 30%, mineral filler 5 ~ 40%, composite antioxidant 0.1 ~ 1%, processing aid 0.1 ~ 1%, mixes in high-speed mixer, can obtain blend after extruding afterwards in twin screw extruder.
Beneficial effect
The polypropylene composite material with excellent shock proof performance of the present invention, the toughness under its normal temperature and low temperature, notched Izod impact strength is excellent, and its thermotolerance and rigidity are also very excellent, therefore have a wide range of applications.The present invention adopts twin screw extruder to carry out extruding pelletization, has shear force large, is conducive to the advantage that toughner and mineral filler disperse in acrylic resin, can improves the toughness of polypropylene material, intensity.The method flow process is simple, continuous, production efficiency is high, constant product quality.
Embodiment
The present invention has the preparation method of the polypropylene composite material of excellent shock proof performance: the first step is by mineral filler at 100 ~ 150 DEG C, dry 1 ~ 5 hour; Mineral filler, polypropylene, toughner, oxidation inhibitor and processing aid drop in high-speed mixer and mix by second step in proportion; Said mixture is sent into twin screw extruder by the 3rd step, and under the conveying and shearing action of screw rod, abundant melting, compound, extrude by head, tie rod, cooling, blower fan dry up, pelletizing, finally pack.
The length-to-diameter ratio of the twin screw extruder machine used in the present invention is at least 36, and each section of extruder temperature controls at 200 DEG C ~ 220 DEG C, and screw speed controls at 200 ~ 400r/min.
Below the specific embodiment of the present invention is described in detail, but it is pointed out that protection scope of the present invention not by the restriction of these embodiments.
Embodiment 1
First by mineral filler CaCO
3in the baking oven of 150 DEG C, drying 2 hours, takes 65 parts of polypropylene, 15 parts of POE, 20 parts of CaCO
3, 0.2 part of composite antioxidant four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (being called for short 1010) and three [2, 4-di-tert-butyl-phenyl] phosphorous acid ester (being called for short 168) (weight ratio 1:1), 0.5 part of processing aid calcium stearate and EBS(weight ratio 1:4) mix in homogenizer after add in twin screw extruder, temperature 140 ~ 220 DEG C, (temperature in each district is respectively 140 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 180 DEG C, lower same, slightly), melt blending is extruded, cooling, pelletizing obtains polypropylene composite material.
Embodiment 2
First by mineral filler CaCO
3in the baking oven of 150 DEG C, drying 2 hours, takes 70 parts of polypropylene, 10 parts of POE, 20 parts of CaCO
3, 0.2 part of antioxidant 1010 and two (2,4-DI-tert-butylphenol compounds) pentaerythritol diphosphites (be called for short 626) (weight ratio 1:1), 0.5 part of processing aid calcium stearate and EBS(weight ratio 1:4) mix in homogenizer after add in twin screw extruder, in temperature 140 ~ 220 DEG C of intervals, melt blending is extruded, is cooled, pelletizing obtains polypropylene composite material.
Embodiment 3
First by mineral filler CaCO
3drying 2 hours in the baking oven of 150 DEG C, take 85 parts of polypropylene, 10 parts of POE, 5 parts of talcum powder, 0.2 part of antioxidant 1010 and 168(weight ratio 1:1), 0.5 part of processing aid calcium stearate and EBS(weight ratio 1:4) mix in homogenizer after add in twin screw extruder, in temperature 140 ~ 220 DEG C of intervals, melt blending is extruded, is cooled, pelletizing obtains polypropylene composite material.
Embodiment 4
First by mineral filler CaCO
3in the baking oven of 150 DEG C, drying 2 hours, takes 75 parts of polypropylene, 5 parts of terpolymer EP rubbers, 20 parts of CaCO
3, 0.2 part of antioxidant 1010 and 168(weight ratio 1:1), 0.5 part of processing aid calcium stearate and EBS(weight ratio 1:4) mix in homogenizer after add in twin screw extruder, in temperature 140 ~ 220 DEG C of intervals, melt blending is extruded, is cooled, pelletizing obtains polypropylene composite material.
Embodiment 5
First by mineral filler CaCO
3in the baking oven of 150 DEG C, drying 2 hours, takes 40 parts of polypropylene, 20 parts of POE, 40 parts of CaCO
3, 0.2 part of antioxidant 1010 and 168(weight ratio 1:1), 0.5 part of processing aid calcium stearate and EBS(weight ratio 1:4) mix in homogenizer after add in twin screw extruder, in temperature 140 ~ 220 DEG C of intervals, melt blending is extruded, is cooled, pelletizing obtains polypropylene composite material.
Embodiment 6
First by mineral filler CaCO
3in the baking oven of 150 DEG C, drying 2 hours, takes 50 parts of polypropylene, 30 parts of POE, 20 parts of CaCO
3, 0.2 part of antioxidant 1010 and 168(weight ratio 1:1), 0.5 part of processing aid calcium stearate and EBS(weight ratio 1:4) mix in homogenizer after add in twin screw extruder, in temperature 140 ~ 220 DEG C of intervals, melt blending is extruded, is cooled, pelletizing obtains polypropylene composite material.
Comparative example 1
Take 90 parts of polypropylene, 10 parts of POE, 1 part of antioxidant 1010 and 168(weight ratio 1:1), 0.1 part of processing aid calcium stearate adds in twin screw extruder after mixing in homogenizer, in temperature 140 ~ 220 DEG C of intervals, melt blending is extruded, is cooled, pelletizing obtains polypropylene composite material.
Comparative example 2
First by mineral filler CaCO
3in the baking oven of 150 DEG C, drying 2 hours, takes 80 parts of polypropylene, 20 parts of CaCO
3, 0.1 part of composite antioxidant 1010 and 168(weight ratio 1:1), 0.5 part of processing aid calcium stearate and EBS(weight ratio 1:4) mix in homogenizer after add in twin screw extruder, in temperature 140 ~ 220 DEG C of intervals, melt blending is extruded, is cooled, pelletizing obtains polypropylene composite material.
Comparative example 3
Take 100 parts of polypropylene, 0.2 part of composite antioxidant 1010 and 168(weight ratio 1:1), 1 part of processing aid calcium stearate and EBS(weight ratio 1:4) mix in homogenizer after add in twin screw extruder, in temperature 140 ~ 220 DEG C of intervals, melt blending is extruded, is cooled, pelletizing obtains polypropylene composite material.
In order to investigate the performance of above each embodiment and comparative example resulting product, the present invention has carried out the test of tensile strength and Young's modulus according to BG/T1040-92 standard to each goods, secondly also tests simply supported beam notched Izod impact strength according to GB/T1834-1996.The results are shown in Table 1.
Table 1
Claims (5)
1. a polypropylene composite material, is characterized in that: integral part is as follows:
(a), acrylic resin 40 ~ 85wt%;
(b), toughner 5 ~ 30wt%;
(c), packing material: 5 ~ 40wt%;
(d), composite antioxidant 0.1 ~ 1wt%;
(e), processing aid 0.1 ~ 1wt%;
Described (a) acrylic resin homo-polypropylene;
Described (b) toughner is the composition of one or more in ethylene-octene copolymer (POE), polyurethane elastomer, polystyrene elastomers, terpolymer EP rubber;
Described (c) packing material selects the one or more combination thing of talcum powder, calcium carbonate, barium sulfate, kaolin, wollastonite, polynite, calcium carbonate crystal whisker;
Described (d) composite antioxidant selects Hinered phenols antioxidant, phosphite antioxidant, sulfur-bearing oxidation inhibitor, complex type antioxidant;
Described (e) processing aid is the one of calcium stearate, ethylene hard acid acyl amine (EBS), or two kinds of mixtures.
2. polypropylene composite material according to claim 1, it is characterized in that: described each compositions in weight percentage is acrylic resin 40 ~ 80%, toughner 5 ~ 25%, mineral filler 10 ~ 40%, composite antioxidant 0.1 ~ 0.5%, processing aid 0.1 ~ 0.8%.
3. polypropylene composite material according to claim 1 and 2, it is characterized in that: described composite antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, three [2,4-di-tert-butyl-phenyl] phosphorous acid ester, two (2,4-DTBP) pentaerythritol diphosphites, two (18) ester of thio-2 acid, the hard alcohol ester composition of thio-2 acid two one or more combination thing.
4. polypropylene composite material according to claim 3, it is characterized in that: it is four [β-(3 that described composite antioxidant is worked as, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three [2,4-di-tert-butyl-phenyl] phosphorous acid ester time, weight ratio is 1:1-1:4.
5. the preparation method of a polypropylene composite material according to claim 1, it is characterized in that, material is weighed: acrylic resin 40 ~ 85% by following weight proportion, toughner 5 ~ 30%, mineral filler 5 ~ 40%, composite antioxidant 0.1 ~ 1%, processing aid 0.1 ~ 1%, mix in high-speed mixer, after extruding in twin screw extruder afterwards, can blend be obtained.
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| CN201410149165.5A CN104974418A (en) | 2014-04-14 | 2014-04-14 | Polyropylene composite material and preparation method thereof |
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| CN201410149165.5A CN104974418A (en) | 2014-04-14 | 2014-04-14 | Polyropylene composite material and preparation method thereof |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519429A (en) * | 2016-10-21 | 2017-03-22 | 宁波尚高新材料有限公司 | Hydrophobic high-elasticity composite material and preparing method thereof |
| CN106674733A (en) * | 2016-12-13 | 2017-05-17 | 安徽省金正塑业有限公司 | Tear-resistant polypropylene plastic |
| CN107383596A (en) * | 2017-07-18 | 2017-11-24 | 合肥华凌股份有限公司 | Hollow sheeting master batch, hollow sheeting and refrigerator |
| CN107973992A (en) * | 2016-10-21 | 2018-05-01 | 合肥杰事杰新材料股份有限公司 | A kind of low temperature resistant, high impact resistance polypropylene composite material and preparation method thereof |
| CN109181116A (en) * | 2018-08-19 | 2019-01-11 | 福建师范大学泉港石化研究院 | A kind of preparation method of high abrasion scratch resistance polypropylene pipe |
| CN109306115A (en) * | 2018-08-24 | 2019-02-05 | 苏州润佳工程塑料股份有限公司 | A kind of PP composite material and preparation method thereof with rubber sense of touch |
| CN111472091A (en) * | 2020-05-07 | 2020-07-31 | 江苏伟创力新材料有限公司 | Three-dimensional facial mask non-woven fabric and manufacturing method thereof |
| CN111518339A (en) * | 2020-05-05 | 2020-08-11 | 陈洁琼 | Low-temperature-resistant reinforced polypropylene plastic pipe and preparation method thereof |
| CN111704767A (en) * | 2019-03-18 | 2020-09-25 | 广州市香港科大霍英东研究院 | High-rigidity high-toughness polypropylene composite material and preparation method thereof |
| CN112111100A (en) * | 2020-08-28 | 2020-12-22 | 安徽越洋达新能源科技有限公司 | Composite plastic for power supply bracket and preparation method thereof |
| CN112358677A (en) * | 2020-10-27 | 2021-02-12 | 上海金发科技发展有限公司 | Super-lubricating polypropylene composition and preparation method thereof |
| CN112457578A (en) * | 2020-11-04 | 2021-03-09 | 盘锦海兴科技股份有限公司 | Wollastonite modified polypropylene master batch and preparation method thereof |
| CN112724527A (en) * | 2020-12-29 | 2021-04-30 | 上海普利特复合材料股份有限公司 | Impact-resistant modified polypropylene blend with controllable phase domain size and preparation method thereof |
| CN113150447A (en) * | 2021-05-21 | 2021-07-23 | 浙江晟祺实业有限公司 | Heat-resistant insulating polymer composite material and preparation method thereof |
| CN114230467A (en) * | 2021-11-30 | 2022-03-25 | 金发科技股份有限公司 | Hindered phenol compound and preparation method and application thereof |
| CN115232399A (en) * | 2022-07-28 | 2022-10-25 | 江苏康宝医疗器械有限公司 | Medical polypropylene material and preparation method thereof |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107973992A (en) * | 2016-10-21 | 2018-05-01 | 合肥杰事杰新材料股份有限公司 | A kind of low temperature resistant, high impact resistance polypropylene composite material and preparation method thereof |
| CN106519429A (en) * | 2016-10-21 | 2017-03-22 | 宁波尚高新材料有限公司 | Hydrophobic high-elasticity composite material and preparing method thereof |
| CN106674733A (en) * | 2016-12-13 | 2017-05-17 | 安徽省金正塑业有限公司 | Tear-resistant polypropylene plastic |
| CN107383596A (en) * | 2017-07-18 | 2017-11-24 | 合肥华凌股份有限公司 | Hollow sheeting master batch, hollow sheeting and refrigerator |
| CN109181116A (en) * | 2018-08-19 | 2019-01-11 | 福建师范大学泉港石化研究院 | A kind of preparation method of high abrasion scratch resistance polypropylene pipe |
| CN109306115A (en) * | 2018-08-24 | 2019-02-05 | 苏州润佳工程塑料股份有限公司 | A kind of PP composite material and preparation method thereof with rubber sense of touch |
| CN111704767A (en) * | 2019-03-18 | 2020-09-25 | 广州市香港科大霍英东研究院 | High-rigidity high-toughness polypropylene composite material and preparation method thereof |
| CN111518339B (en) * | 2020-05-05 | 2022-12-16 | 上海齐润新材料有限公司 | Low-temperature-resistant reinforced polypropylene plastic pipe and preparation method thereof |
| CN111518339A (en) * | 2020-05-05 | 2020-08-11 | 陈洁琼 | Low-temperature-resistant reinforced polypropylene plastic pipe and preparation method thereof |
| CN111472091A (en) * | 2020-05-07 | 2020-07-31 | 江苏伟创力新材料有限公司 | Three-dimensional facial mask non-woven fabric and manufacturing method thereof |
| CN112111100A (en) * | 2020-08-28 | 2020-12-22 | 安徽越洋达新能源科技有限公司 | Composite plastic for power supply bracket and preparation method thereof |
| CN112358677A (en) * | 2020-10-27 | 2021-02-12 | 上海金发科技发展有限公司 | Super-lubricating polypropylene composition and preparation method thereof |
| CN112457578A (en) * | 2020-11-04 | 2021-03-09 | 盘锦海兴科技股份有限公司 | Wollastonite modified polypropylene master batch and preparation method thereof |
| CN112457578B (en) * | 2020-11-04 | 2023-12-19 | 盘锦海兴科技股份有限公司 | Wollastonite modified polypropylene master batch and preparation method thereof |
| CN112724527A (en) * | 2020-12-29 | 2021-04-30 | 上海普利特复合材料股份有限公司 | Impact-resistant modified polypropylene blend with controllable phase domain size and preparation method thereof |
| CN113150447A (en) * | 2021-05-21 | 2021-07-23 | 浙江晟祺实业有限公司 | Heat-resistant insulating polymer composite material and preparation method thereof |
| CN114230467A (en) * | 2021-11-30 | 2022-03-25 | 金发科技股份有限公司 | Hindered phenol compound and preparation method and application thereof |
| WO2023098473A1 (en) * | 2021-11-30 | 2023-06-08 | 金发科技股份有限公司 | Hindered phenolic compound, preparation method therefor and use thereof |
| CN114230467B (en) * | 2021-11-30 | 2023-10-31 | 金发科技股份有限公司 | Hindered phenol compound and preparation method and application thereof |
| CN115232399A (en) * | 2022-07-28 | 2022-10-25 | 江苏康宝医疗器械有限公司 | Medical polypropylene material and preparation method thereof |
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