CN105837932A - Preparation method for crystal polypropylene resin composition - Google Patents
Preparation method for crystal polypropylene resin composition Download PDFInfo
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- CN105837932A CN105837932A CN201610195906.2A CN201610195906A CN105837932A CN 105837932 A CN105837932 A CN 105837932A CN 201610195906 A CN201610195906 A CN 201610195906A CN 105837932 A CN105837932 A CN 105837932A
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- polypropylene resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
- C08L2205/24—Crystallisation aids
- C08L2205/242—Beta spherulite nucleating agents
Abstract
The invention relates to a preparation method for a crystal polypropylene resin composition. The preparation method comprises the following steps: (1) uniformly mixing reaction monomer with polypropylene matrix resin; and (2) extruding the mixed polypropylene resin with a screw extruder so as to obtain the polypropylene resin composition, or subjecting the mixed polypropylene resin to injection molding, blow molding, compression molding, rotational molding, slush molding or plastic extrusion so as to prepare the polypropylene resin composition. In the process of extrusion in the invention, different reaction monomers react with each other in a polypropylene melt to produce a new nucleating agent which induces nucleation and crystallization of polypropylene and improves crystallization performance and macroscopic applicability of polypropylene. The nucleating agent prepared in situ during processing has higher nucleation efficiency and more protruding performance improvement effect compared with individually added nucleating agents.
Description
Technical field
The invention belongs to acrylic resin and preparing technical field thereof, former particularly to passing through in the acrylic resin course of processing
Position preparation and interpolation nucleator, to improve the nucleation efficiencies of nucleator, prepare crystalline polypropylene resin compositions.
Background technology
Polypropylene (PP) from nineteen fifty-seven by Italy since Meng Tekadini (Montecatini) company realizes its industrialization, because of
It has good mechanical property, nontoxic, relative density is low, heat-resisting, chemical-resistant resistance, is easily worked the good characteristics such as molding,
And cheap, its production has obtained swift and violent development, it has also become in five big general synthetic resins, growth rate is the fastest, new product
Plant the kind that exploitation is the most active.Although polypropylene advantage is numerous, but in place of there is also some shortcomings, as fragile under low temperature disconnected,
Shrinkage factor is big, and creep resistance is poor, fast light, hot and ageing resistace is poor, thus have impact on its application in wide range of areas.
In order to improve polyacrylic macro property, expand polyacrylic application, it is necessary to polypropylene is modified.Add nucleation
Agent has become as the most active, the most the most frequently used PP high performance owing to its modified effect is good, simple, with low cost
One of method.
The nucleator that the nucleator being used widely in the industry at present and researcher are researching and developing broadly falls into thing
Reason addition type, i.e. nucleator join in polypropylene matrix in the course of processing, nucleator induction during crystalling propylene
Polypropylene nucleation and crystallization, nucleator is as becoming nuclear particle induction crystalling propylene in the process, and molecular structure own does not occurs
Change, nucleation process belongs to physical process.On the one hand nucleation efficiencies and the impact micromorphologic on polypropylene of nucleator take
Certainly in the structure of nucleator itself, depend on into the quantity of nuclear particle simultaneously.For a kind of nucleator determined, nucleation
The quantity of agent particle is the key factor determining nucleation efficiencies.Add equal in quality and divide the nucleator of rate, become the quantity of nuclear particle
The most, its nucleation efficiencies is the highest.It is understood that become the quantity of nuclear particle to depend on size and the distribution of nucleator.Institute
Make the particle diameter of nucleator be distributed more homogenization with the particle diameter of reduction nucleator simultaneously and just become raising existing nucleator effect
The most efficient method of rate, is also the focus of current nucleator research field.
In order to improve the efficiency of nucleator, improve polyacrylic macroscopic view application performance, reduce polypropylene production and processing cost, section
The worker that grinds is prepared as nanoscale nucleator, is then added in polypropylene matrix, and result of study shows nano level nucleation
Agent improves nucleation efficiencies the most to a certain extent, but effect is not very notable, and its reason essentially consists in nano level one-tenth
Core agent is easily reunited in polypropylene matrix, causes declining to a great extent of nucleation efficiencies.
By up to the present, nucleator scattering problem in polypropylene is not the most well solved.So, have
Necessary research improves nucleator dispersibility in polypropylene and improves the new method of nucleation efficiencies further.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that the preparation side of a kind of crystalline polypropylene resin compositions
Method.The preparation method of the present invention is in extrusion, and differential responses monomer carries out reaction in melt polypropylene and generates new one-tenth
Core agent, induces polypropylene nucleation and crystallization, improves polyacrylic crystal property, improves polyacrylic macroscopic view application performance energy.Should
The nucleator that the nucleator ratio prepared with this course of processing situ individually adds, nucleation efficiencies is higher, on performance improvement
The most prominent.
The purpose of the present invention is achieved through the following technical solutions:
It is an object of the invention to provide the preparation method of a kind of crystalline polypropylene resin compositions, including:
(1) reaction monomers is uniform with polypropylene matrix mixed with resin, wherein, described reaction monomers is carboxylic acid or acid
Acid anhydride and metal-oxide or the mixture of metal hydroxides；
(2) mixed acrylic resin is extruded on screw extruder by a., prepares polypropylene resin composite；
Or mixed acrylic resin is carried out being molded, is blow molded by b., compression moulding, rotational moulding, slush moulding or extrusion molding, prepare poly-
Propylene resin composition；
Further, described anhydride is benzoyl oxide, phthalic anhydride, equal benzoyl oxide, glutaric anhydride, adipic acid
Acid anhydride, 1,5-pentanedicarboxylic acid. acid anhydride or suberic acid acid anhydride；Described carboxylic acid be benzoic acid, phthalic acid, Pyromellitic Acid, 1,3-propanedicarboxylic acid, oneself
Diacid, 1,5-pentanedicarboxylic acid. or suberic acid.
Further, described metal-oxide is aluminium oxide, zinc oxide or calcium oxide；Described metal hydroxides is hydrogen
Aluminium oxide, zinc hydroxide or calcium hydroxide.
Further, described step (1) also includes adding one or more in antioxidant, processing aid, filler.
Further, described antioxidant is selected from phosphite antioxidant 168, hindered phenol antioxygen 1010, hindered phenol antioxygen
1098, one or both in hindered phenol antioxygen 1076.
Further, one or more during described filler is nanoclay, calcium carbonate, Pulvis Talci.
Further, the polypropylene matrix resin in described step (1) is HOPP or COPP；Preferably etc.
Rule HOPP.
Further, the extrusion temperature of the screw extruder in described step (2) a is 180-250 DEG C, and screw speed is 50-500
Rev/min.
The preparation method of the present invention is in extrusion, and differential responses monomer (nucleator monomer) is carried out in melt polypropylene
Reaction, generates new nucleator, induces polypropylene nucleation and crystallization, improves polyacrylic crystal property, improve polyacrylic grand
See application performance energy, thus prepare the polypropylene resin composite containing this nucleator.
Compared with prior art, the positive effect of the present invention is as follows:
1, the present invention adds two or more reaction monomers (nucleator monomer) in the course of processing, is allowed in the course of processing
Middle generation chemical reaction and generate a kind of efficient polypropylene nucleater, newly-generated nucleator is tied in melt polypropylene again
Crystalline substance, new crystal particle diameter is less and particle diameter distribution is more uniform, has good dispersibility in polypropylene matrix, it is possible to
The nucleation efficiencies of nucleator is greatly improved, the most effectively solves the problem that nucleator is reunited.
2, applying nucleator prepared by this course of processing situ than the nucleator individually added, nucleation efficiencies is higher,
On performance improvement the most prominent.
Accompanying drawing explanation
Fig. 1 is blank polypropylene, comparative example 1 and the DSC crystallization curve of the polypropylene specimen prepared by embodiment 1；
Fig. 2 is blank polypropylene, comparative example 2 and the DSC crystallization curve of the polypropylene specimen prepared by embodiment 2；
Fig. 3 is blank polypropylene, comparative example 3 and the DSC crystallization curve of the polypropylene specimen prepared by embodiment 3；
Fig. 4 is blank polypropylene, comparative example 4 and the DSC crystallization curve of the polypropylene specimen prepared by embodiment 4.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, art technology
The present invention can be made various changes or modifications by personnel, and these equivalent form of values fall within the application appended claims equally and limited
Fixed scope.
Embodiment 1
Alpha-crystal form nucleator aluminum benzoate original position in isotactic HOPP is prepared and adds:
3.6 grams of benzoic acid (molecular weight 123) are uniformly mixed with 1 gram of aluminium oxide (molecular weight 102), then resists with 1 gram
Oxygen agent 1010 and 1 gram of irgasfos 168,1000 grams of isotactic polypropylene (raising sub-petrochemical industry, the trade mark is F401) powders mix at height
Mix homogeneously in machine, joins this mixture in double screw extruder (screw slenderness ratio is 30) and extrudes, be prepared into
To the polypropylene resin composite containing aluminum benzoate alpha-crystal form nucleator, then it is molded into standard batten (ASTM standard),
Polyacrylic stretching and bending property are tested.
Procession parameters is as follows:
Table 1 nucleated polypropylene extruding pelletization condition
The technological parameter of injection is as follows:
Table 2 nucleated polypropylene injecting condition
Comparative example 1
Simultaneously as contrast, 4.7 grams of aluminum benzoates are added in 1000 grams of polypropylene directly as nucleator and carries out twin screw
Extrusion, remaining, with embodiment 1, prepares the polypropylene resin composite containing aluminum benzoate.
Tensile property and the bending property of polypropene composition are tested by application tensilon.Tensile property presses ASTM
D638-2003 tests, and rate of extension is 20mm/min；Bending property is tested by ASTM D790-2003, curved
Bent speed is 10mm/min；
Impact property is tested by ASTM D256-2006.Acrylic resin is combined by application differential scanning calorimeter (DSC)
The Crystallization peak temperature of thing carries out characterizing (DSC temperature rate is 10 DEG C/min).Concrete outcome is as shown in Fig. 1 and Biao 3.
Table 3
From table 3 it is observed that aluminum benzoate is as effective polypropylene alpha-crystal form nucleator, it is added directly into polypropylene
In, it is possible to effective raising crystalling propylene peak temperature, transparency and rigidity (hot strength and bending modulus).With sky
White polypropylene is compared, and Crystallization peak temperature improves 5 DEG C, and mist degree reduces 21.3%, and hot strength and bending modulus are respectively
Improve 7.4% and 10.2%.But the course of processing situ synthesis aluminum benzoate for polypropylene transparent and rigidity
Increase rate bigger, nucleation efficiencies is higher.With blank polypropylene ratio, Crystallization peak temperature improves 7.2 DEG C, and mist degree drops
Low by 44.4%, hot strength and bending modulus have been respectively increased 11.2% and 21.0%.Contrast directly add aluminum benzoate with
The effect of course of processing situ synthesizing benzoic acids aluminum is it can be seen that the nucleation effect of aluminum benzoate of course of processing situ synthesis
Fruit is substantially better than the aluminum benzoate of directly interpolation.
Embodiment 2
Beta crystal-type nucleater adipic acid zinc is prepared in the original position of isotactic HOPP and adds
2.9 g of adipic acid (molecular weight: 146) are uniformly mixed in mortar with 1.6 grams of zinc oxide (molecular weight: 81),
Then with 1 gram of antioxidant 1010 and 1 gram of irgasfos 168,1000 grams of isotactic polypropylene (raising sub-petrochemical industry, the trade mark is F401)
Powder uniformly mixes in high mixer, is joined by this mixture in double screw extruder and carries out extruding that (procession parameters is detailed
It is shown in Table 1), prepare the polypropylene resin composite containing adipic acid zinc beta crystal-type nucleater, then injection (injection work
Skill parameter refers to table 2) become standard batten (ASTM standard), polyacrylic shock resistance is tested.
Comparative example 2
Simultaneously as contrast, 4.2 g of adipic acid zinc are added to directly as nucleator polypropylene carry out twin-screw extrusion,
Remaining, with embodiment 2, prepares the polypropylene resin composite containing adipic acid zinc.
The shock resistance of polypropene composition is tested by application shock machine, and impact property presses ASTM
D256-2006 standard is tested.Application differential scanning calorimeter (DSC) peak crystallization to this polypropylene resin composite
Value temperature carries out characterizing (DSC temperature rate is 10 DEG C/min)；Application X-ray diffraction is brilliant to the β of polypropene composition
Type content is analyzed (test sample after thermal station hot pressing in 125 DEG C of isothermal crystals 30 minutes), concrete outcome such as Fig. 2 and Biao
Shown in 4.
According to X-ray diffraction principle, different crystalline structures, cause the position that crystalline high polymer characteristic diffraction peak occurs
Put difference, thus may determine which kind of crystal formation PP belongs to, and various crystal formation can be calculated according to the height of diffraction maximum
Content.In the range of the 2 θ angles of diffraction of 6-25 °, 5 main diffraction peak of alpha-crystal form, lay respectively at 14.1 °, 16.8 °,
At 18.6 °, 21.2 ° and 21.8 °, it is corresponding in turn to the crystal face such as (110), (040), (130) and overlapping (131) and (111)
The diffraction maximum produced, this is the diffraction maximum feature of typical case's alpha-crystal form polypropylene.Beta crystal is to occur in that at 16.08 ° at 2 θ
(300) crystallographic plane diffraction peak of typical beta crystal feature.
According to Turner-Jon formula (formula 1), the relative amount (k value) of beta crystal can be calculated:
K=H (300)/[H (300)+H (110)+H (040)+H (130)] × 100% (1)
In formula, H (300) is the peak height in face, β crystalline substance peak (300), and H (110), H (040) and H (130) are respectively the face, peak that α is brilliant
(110), (040) and the peak height of (130).
Table 4
As can be seen from Table 4, adipic acid zinc is as effective polypropylene beta crystal nucleating agent, and it is added directly into polypropylene
In, it is possible to the polyacrylic Crystallization peak temperature of effective raising, beta-crystalline form content and toughness (impact strength).With sky
White polypropylene is compared, and Crystallization peak temperature improves 6.6 DEG C, and beta-crystalline form content is 0.64, and impact strength improves 76%.
But the course of processing situ synthesis adipic acid zinc for crystalling propylene peak temperature, beta-crystalline form content and shock resistance
Intensity increase rate is bigger, and nucleation efficiencies is higher.With blank polypropylene ratio, Crystallization peak temperature improves 11 DEG C, beta crystal
Content is 0.97, and impact strength improves 232%.Adipic acid zinc is directly added in contrast and the synthesis of course of processing situ is own
The effect of diacid zinc is it can be seen that the nucleating effect of adipic acid zinc of course of processing situ synthesis is substantially better than and directly adds oneself
Diacid zinc.
Embodiment 3
Alpha-crystal form nucleator aluminum benzoate original position preparation in isotactic HOPP and adding, and and nanoclay compound:
3.6 grams of benzoic acid (molecular weight 123) are uniformly mixed with 1 gram of aluminium oxide (molecular weight 102), then resists with 1 gram
Oxygen agent 1010 and 1 gram of irgasfos 168,50 grams of nanoclays (product designation 1.44P, Nanocor company of the U.S.),
1000 grams of isotactic polypropylene (raising sub-petrochemical industry, the trade mark is F401) powders are uniform in high-speed mixer and mixing, added by this mixture
Enter in double screw extruder to carry out to extrude (expressing technique refers to table 1), prepare containing aluminum benzoate alpha-crystal form nucleation
The polypropylene resin composite of agent, then injection (Shooting Technique refers to table 2) becomes standard batten (ASTM standard), right
Polyacrylic stretching and bending property are tested.
Comparative example 3
Simultaneously as contrast, 4.7 grams of aluminum benzoates are added in 1000 grams of polypropylene directly as nucleator and carries out twin screw
Extrusion, remaining, with embodiment 3, prepares the polypropylene resin composite containing aluminum benzoate.
Tensile property and the bending property of polypropene composition are tested by application tensilon, apply shock machine pair
Shock resistance is tested.Tensile property is tested by ASTM D638-2003, and rate of extension is 20mm/min；Curved
Qu Xingneng is tested by ASTM D790-2003, and bending speed is 10mm/min；Impact property presses ASTM D256-2006
Test；Application differential scanning calorimeter (DSC) characterizes (DSC to the Crystallization peak temperature of polypropylene resin composite
Temperature rate is 10 DEG C/min), concrete outcome is as shown in fig. 3 and table 5.
Table 5
As can be seen from Table 5, aluminum benzoate, as effective polypropylene alpha-crystal form nucleator, is added directly in polypropylene
And carry out compound use with nanoclay, it is possible to effective improve crystalling propylene peak temperature, rigidity (hot strength and curved
Bent modulus) and toughness (impact strength).Compared with blank polypropylene, Crystallization peak temperature improves 5.4 DEG C, stretching
Intensity and bending modulus have been respectively increased 7.2% and 19.8%, and impact strength improves 18.4%.But in the course of processing
The raising for polyacrylic Crystallization peak temperature, rigidity and toughness after compound of the aluminum benzoate of situ synthesis and nanoclay
Amplitude is bigger, and nucleation efficiencies is higher.With blank polypropylene ratio, Crystallization peak temperature improves 8 DEG C, hot strength and bending
Modulus has been respectively increased 12.5% and 31.2%, and impact strength improves 26.3%.Contrast is directly added aluminum benzoate and adds
Effect that during work, fabricated in situ aluminum benzoate is compound with nanoclay respectively is it can be seen that the synthesis of course of processing situ
The nucleating effect of aluminum benzoate is substantially better than the aluminum benzoate of directly interpolation.
Embodiment 4
Beta crystal-type nucleater adipic acid zinc original position in COPP is prepared and adds
2.9 g of adipic acid (molecular weight: 146) are uniformly mixed in mortar with 1.6 grams of zinc oxide (molecular weight: 81),
Then with 1 gram of antioxidant 1010 and 1 gram of irgasfos 168, (raising sub-petrochemical industry, the trade mark is 1000 grams of COPP powders
C180) uniform in high-speed mixer and mixing, this mixture is joined in double screw extruder and carry out extruding that (expressing technique refers to
Table 1), prepare the polypropylene resin composite containing adipic acid zinc beta crystal-type nucleater, then injection (Shooting Technique
Refer to table 2) become standard batten (ASTM standard), polyacrylic shock resistance is tested.
Comparative example 4
Simultaneously as contrast, 4.2 g of adipic acid zinc are added to directly as nucleator polypropylene carry out twin-screw extrusion,
Remaining, with embodiment 4, prepares the polypropylene resin composite containing adipic acid zinc.
The shock resistance of polypropene composition is carried out testing impact property by ASTM D256-2006 by application shock machine
Test；The Crystallization peak temperature of this polypropylene resin composite is characterized by application differential scanning calorimeter (DSC)
(DSC temperature rate is 10 DEG C/min)；The beta-crystalline form content of polypropene composition is carried out point by application X-ray diffraction
Analysis (test sample after thermal station hot pressing in 125 DEG C of isothermal crystals 30 minutes), concrete outcome is as shown in Fig. 4 and Biao 6.
Table 6
As can be seen from Table 6, adipic acid zinc, as effective beta crystal-type nucleater, can effectively improve after directly adding
The Crystallization peak temperature of COPP, beta-crystalline form content and toughness (impact strength).With blank COPP phase
Ratio, Crystallization peak temperature improves 3.8 DEG C, and beta-crystalline form content is 0.81, and impact strength improves 67%.But adding
During work, the adipic acid zinc of fabricated in situ improves for crystalling propylene peak temperature, beta-crystalline form content and impact strength
Amplitude is bigger, and nucleation efficiencies is higher.With blank COPP ratio, Crystallization peak temperature improves 6.6 DEG C, and beta crystal contains
Amount is 0.92, and impact strength improves 105%.Adipic acid zinc is directly added in contrast and course of processing situ synthesizes oneself two
The effect of acid zinc is it can be seen that the nucleating effect of adipic acid zinc of course of processing situ synthesis is substantially better than and directly adds oneself two
Acid zinc.
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.The technology people of the industry
Member, it should be appreciated that the present invention is not restricted to the described embodiments, simply illustrates this described in above-described embodiment and description
Bright principle, the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, these changes
Both fall within scope of the claimed invention with improvement.Claimed scope by appending claims and etc.
Jljl is defined.
Claims (8)
1. a preparation method for crystalline polypropylene resin compositions, including:
(1) reaction monomers is uniform with polypropylene matrix mixed with resin, wherein, described reaction monomers is carboxylic acid or acid
Acid anhydride and metal-oxide or the mixture of metal hydroxides；
(2) mixed acrylic resin is extruded on screw extruder by a., prepares polypropylene resin composite；
Or mixed acrylic resin is carried out being molded, is blow molded by b., compression moulding, rotational moulding, slush moulding or extrusion molding, prepare poly-
Propylene resin composition.
The preparation method of a kind of crystalline polypropylene resin compositions the most according to claim 1, it is characterised in that: described acid
Acid anhydride is benzoyl oxide, phthalic anhydride, equal benzoyl oxide, glutaric anhydride, adipic anhydride, 1,5-pentanedicarboxylic acid. acid anhydride or suberic acid acid anhydride；
Described carboxylic acid is benzoic acid, phthalic acid, Pyromellitic Acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid. or suberic acid.
The preparation method of a kind of crystalline polypropylene resin compositions the most according to claim 1, it is characterised in that: described gold
Genus oxide is aluminium oxide, zinc oxide or calcium oxide；Described metal hydroxides is aluminium hydroxide, zinc hydroxide or hydrogen-oxygen
Change calcium.
The preparation method of a kind of crystalline polypropylene resin compositions the most according to claim 1, it is characterised in that: described step
(1) the polypropylene matrix resin in is isotactic HOPP.
The preparation method of a kind of crystalline polypropylene resin compositions the most according to claim 1, it is characterised in that: described step
(1) also include adding one or more in antioxidant, processing aid, filler.
The preparation method of a kind of crystalline polypropylene resin compositions the most according to claim 5, it is characterised in that: described antioxygen
Agent is selected from phosphite antioxidant 168, hindered phenol antioxygen 1010, hindered phenol antioxygen 1098, hindered phenol antioxygen 1076
In one or both.
The preparation method of a kind of crystalline polypropylene resin compositions the most according to claim 5, it is characterised in that: described filler
For one or more in nanoclay, calcium carbonate, Pulvis Talci.
The preparation method of a kind of crystalline polypropylene resin compositions the most according to claim 1, it is characterised in that: described step
(2) extrusion temperature of the screw extruder in a is 180-250 DEG C, and screw speed is 50-500 rev/min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836618A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | A kind of method of modifying of aluminium oxide |
| CN110951151A (en) * | 2019-12-04 | 2020-04-03 | 苏州炜隆灿防静电包装有限公司 | Preparation method of high-strength high-toughness polypropylene composite material |
| CN112159594A (en) * | 2020-09-25 | 2021-01-01 | 华东理工大学 | Cage type silsesquioxane nucleating agent and preparation method and application thereof |
| CN113831646A (en) * | 2021-09-08 | 2021-12-24 | 南京雷泰克材料科技有限公司 | Preparation method of polypropylene foam |
| CN114806024A (en) * | 2022-05-05 | 2022-07-29 | 横店集团得邦工程塑料有限公司 | High-impact-resistance low-temperature-resistance polypropylene material and preparation method thereof |
| CN115584054A (en) * | 2022-10-21 | 2023-01-10 | 中国石油化工股份有限公司 | Polypropylene beta-crystal nucleating agent composition and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100465A (en) * | 1985-04-01 | 1986-07-09 | 中国科学院上海有机化学研究所 | Beta-crystalline polyacrylic, production method and application |
| CN102086280A (en) * | 2009-12-04 | 2011-06-08 | 中国石油化工股份有限公司 | Preparation method of polypropylene nano composite material |
-
2016
- 2016-03-31 CN CN201610195906.2A patent/CN105837932B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100465A (en) * | 1985-04-01 | 1986-07-09 | 中国科学院上海有机化学研究所 | Beta-crystalline polyacrylic, production method and application |
| CN102086280A (en) * | 2009-12-04 | 2011-06-08 | 中国石油化工股份有限公司 | Preparation method of polypropylene nano composite material |
Non-Patent Citations (2)
| Title |
|---|
| R.根赫特等: "《塑料添加剂手册》", 31 January 2000, 化学工业出版社 * |
| 周祥兴: "《合成树脂新资料手册》", 31 May 2002, 中国物资出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836618A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | A kind of method of modifying of aluminium oxide |
| CN109836618B (en) * | 2017-11-28 | 2021-03-30 | 中国石油天然气股份有限公司 | Modification method of aluminum oxide |
| CN110951151A (en) * | 2019-12-04 | 2020-04-03 | 苏州炜隆灿防静电包装有限公司 | Preparation method of high-strength high-toughness polypropylene composite material |
| CN112159594A (en) * | 2020-09-25 | 2021-01-01 | 华东理工大学 | Cage type silsesquioxane nucleating agent and preparation method and application thereof |
| CN113831646A (en) * | 2021-09-08 | 2021-12-24 | 南京雷泰克材料科技有限公司 | Preparation method of polypropylene foam |
| CN114806024A (en) * | 2022-05-05 | 2022-07-29 | 横店集团得邦工程塑料有限公司 | High-impact-resistance low-temperature-resistance polypropylene material and preparation method thereof |
| CN115584054A (en) * | 2022-10-21 | 2023-01-10 | 中国石油化工股份有限公司 | Polypropylene beta-crystal nucleating agent composition and application thereof |
| CN115584054B (en) * | 2022-10-21 | 2024-03-29 | 中国石油化工股份有限公司 | Polypropylene beta-crystal nucleating agent composition and application thereof |
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