CN105837932B - A kind of preparation method of crystalline polypropylene resin composition - Google Patents
A kind of preparation method of crystalline polypropylene resin composition Download PDFInfo
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- CN105837932B CN105837932B CN201610195906.2A CN201610195906A CN105837932B CN 105837932 B CN105837932 B CN 105837932B CN 201610195906 A CN201610195906 A CN 201610195906A CN 105837932 B CN105837932 B CN 105837932B
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- 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
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Abstract
The present invention relates to a kind of preparation methods of crystalline polypropylene resin composition, comprising: (1) is uniformly mixed reaction monomers with polypropylene matrix resin；(2) mixed acrylic resin is squeezed out on screw extruder, polypropylene resin composite is made；Or mixed acrylic resin is molded, is blow molded, compression moulding, rotational moulding, slush moulding or extrusion molding, polypropylene resin composite is made.In extrusion process, differential responses monomer carries out reaction in melt polypropylene and generates new nucleating agent preparation method of the invention, induces polypropylene nucleation and crystallization, improves polyacrylic crystal property, improves polyacrylic macroscopical application performance energy.Using the nucleating agent being prepared in situ in this process than the nucleating agent individually added, nucleation efficiencies are higher, more prominent on performance improvement.
Description
Technical field
The invention belongs to acrylic resin and its preparation technical fields, in particular to lead in acrylic resin process
It crosses and is prepared in situ and adds nucleating agent, to improve the nucleation efficiencies of nucleating agent, crystalline polypropylene resin composition is made.
Background technique
Polypropylene (PP) from nineteen fifty-seven by Italian Meng Tekadini (Montecatini) company realize its industrialization with
Come, because it is with good mechanical property, nontoxic, relative density is low, heat-resisting, chemical-resistant resistance, is easily worked the good characteristics such as molding,
And it is cheap, production has obtained swift and violent development, it has also become growth rate is most fast in five big general synthetic resins, new varieties
Develop kind the most active.Although polypropylene advantage is numerous, there is also some shortcomingss, such as fragile under low temperature disconnected, shrink
Rate is big, and creep resistance is poor, and fast light, hot and anti-aging property is poor, to affect it in the application of wide range of areas.In order to improve
Polyacrylic macro property expands polyacrylic application field, it is necessary to be modified to polypropylene.Addition nucleating agent changes due to it
Property good, simple and easy, low in cost one of the method for having become current most active, most common PP high performance of effect.
The nucleating agent that the nucleating agent and researcher being used widely in the industry at present are researching and developing is all
Belong to physics addition type, i.e. nucleating agent is added in polypropylene matrix in process, is nucleated during crystalling propylene
Agent induces polypropylene nucleation and crystallization, and nucleating agent, which is used as, in the process induces crystalling propylene, molecular structure itself at nuclear particle
It does not change, nucleation process belongs to physical process.The nucleation efficiencies of nucleating agent and influence one to polypropylene micromorphology
Aspect depends on the structure of nucleating agent itself, while depending on the quantity at nuclear particle.For a kind of nucleating agent of determination,
The quantity of nucleating agent particle is to determine the key factor of nucleation efficiencies.The nucleating agent of identical mass fraction is added, at nuclear particle
Quantity is more, and nucleation efficiencies are higher.It is understood that depending on the particle size and distribution of nucleating agent at the quantity of nuclear particle.
So the partial size for reducing nucleating agent, which becomes particle diameter distribution more uniformization of nucleating agent just, improves existing nucleating agent
The most efficient method of efficiency, and the hot spot of nucleating agent research field at present.
In order to improve the efficiency of nucleating agent, the polyacrylic macroscopical application performance of improvement reduces polypropylene and produces and processes cost,
Nucleating agent is prepared into nanoscale by researcher, is then added in polypropylene matrix, result of study show nanoscale at
Core agent improves nucleation efficiencies to a certain extent really, but effect is not very significantly, and reason essentially consists in nanoscale
Nucleating agent is easily reunited in polypropylene matrix, leads to declining to a great extent for nucleation efficiencies.
By up to the present, the dispersion of the nucleating agent in polypropylene is not still well solved.So
It is necessary to study the new methods for improving dispersibility of the nucleating agent in polypropylene with further increasing nucleation efficiencies.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of preparations of crystalline polypropylene resin composition
Method.In extrusion process, differential responses monomer carries out reaction in melt polypropylene and generates newly preparation method of the invention
Nucleating agent induces polypropylene nucleation and crystallization, improves polyacrylic crystal property, improves polyacrylic macroscopical application performance energy.It answers
With the nucleating agent being prepared in situ in this process than the nucleating agent individually added, nucleation efficiencies are higher, on performance improvement
It is more prominent.
The purpose of the present invention is achieved through the following technical solutions:
The purpose of the present invention is to provide a kind of preparation methods of crystalline polypropylene resin composition, comprising:
(1) reaction monomers are uniformly mixed with polypropylene matrix resin, wherein the reaction monomers are carboxylic acid or acid
The mixture of acid anhydride and metal oxide or metal hydroxides；
(2) a. squeezes out mixed acrylic resin on screw extruder, and polypropylene resin composite is made；
Or mixed acrylic resin is molded, is blow molded by b., compression moulding, rotational moulding, slush moulding or extrusion molding, and polypropylene is made
Resin combination；
Further, the acid anhydrides is benzoyl oxide, phthalic anhydride, equal benzoyl oxide, glutaric anhydride, adipic acid
Acid anhydride, pimelic acid acid anhydride or suberic anhydride；The carboxylic acid be benzoic acid, phthalic acid, Pyromellitic Acid, glutaric acid, adipic acid,
Pimelic acid or suberic acid.
Further, the metal oxide is aluminium oxide, zinc oxide or calcium oxide；The metal hydroxides is
Aluminium hydroxide, zinc hydroxide or calcium hydroxide.
Further, the step (1) further includes being added selected from one or more of antioxidant, processing aid, filler.
Further, the antioxidant is selected from phosphite antioxidant 168, hindered phenol antioxygen 1010, hindered phenol antioxygen
One or both of agent 1098, hindered phenol antioxygen 1076.
Further, the filler is one or more of nanoclay, calcium carbonate, talcum powder.
Further, the polypropylene matrix resin in the step (1) is homopolypropylene or copolymer polypropylene；It is preferred that etc.
Advise homopolypropylene.
Further, the extrusion temperature of the screw extruder in step (2) a is 180-250 DEG C, and screw speed is
50-500 revs/min.
Preparation method of the invention in extrusion process, differential responses monomer (nucleating agent monomer) in melt polypropylene into
Row reaction, generates new nucleating agent, induces polypropylene nucleation and crystallization, improves polyacrylic crystal property, improves polyacrylic macro
Application performance energy is seen, to prepare the polypropylene resin composite containing this nucleating agent.
Compared with prior art, the positive effect of the present invention is as follows:
1, two or more reaction monomers (nucleating agent monomer) are added in the present invention in process, are allowed in process
Middle generation chemically reacts and generates a kind of efficient polypropylene nucleater, and newly-generated nucleating agent is tied again in melt polypropylene
Crystalline substance, new crystal particle diameter is smaller and particle diameter distribution is more uniform, has good dispersibility, Neng Gou great in polypropylene matrix
Width improves the nucleation efficiencies of nucleating agent, while effectively solving the problems, such as that nucleating agent is reunited.
2, using the nucleating agent being prepared in situ in this process than the nucleating agent individually added, nucleation efficiencies are higher,
It is more prominent on performance improvement.
Detailed description of the invention
Fig. 1 is the DSC crystallization curve of blank polypropylene, polypropylene specimen prepared by comparative example 1 and embodiment 1；
Fig. 2 is the DSC crystallization curve of blank polypropylene, polypropylene specimen prepared by comparative example 2 and embodiment 2；
Fig. 3 is the DSC crystallization curve of blank polypropylene, polypropylene specimen prepared by comparative example 3 and embodiment 3；
Fig. 4 is the DSC crystallization curve of blank polypropylene, polypropylene specimen prepared by comparative example 4 and embodiment 4.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
It alpha-crystal form nucleating agent aluminum benzoate being prepared in situ in isotactic homopolypropylene and adds:
3.6 grams of benzoic acid (molecular weight 123) are uniformly mixed with 1 gram of aluminium oxide (molecular weight 102), then with 1 gram of antioxygen
Agent 1010 and 1 gram irgasfos 168,1000 grams of isotactic polypropylene (Yangtze petrochemical industry, trade mark F401) powders are in high-speed mixer and mixing
Uniformly, this mixture is added in double screw extruder (screw slenderness ratio 30) and is squeezed out, is prepared containing benzene first
Then the polypropylene resin composite of sour aluminium alpha-crystal form nucleating agent is molded into standard batten (ASTM standard), to polyacrylic stretching
It is tested with bending property.
Procession parameters are as follows:
1 nucleated polypropylene extruding pelletization condition of table
The technological parameter of injection molding is as follows:
2 nucleated polypropylene injecting condition of table
Comparative example 1
Simultaneously as a comparison, 4.7 grams of aluminum benzoates are added to progress pair in 1000 grams of polypropylene directly as nucleating agent
Screw Extrusion, remaining prepares the polypropylene resin composite containing aluminum benzoate with embodiment 1.
It is tested using tensile property and bending property of the tensilon to polypropene composition.Tensile property is pressed
ASTMD638-2003 is tested, rate of extension 20mm/min；Bending property is tested by ASTM D790-2003, curved
Bent rate is 10mm/min；
Impact property is tested by ASTM D256-2006.Using differential scanning calorimeter (DSC) to acrylic resin
The Crystallization peak temperature of composition is characterized (DSC temperature rate is 10 DEG C/min).Concrete outcome is as shown in Fig. 1 and table 3.
Table 3
From table 3 it is observed that aluminum benzoate is added directly into poly- third as effective polypropylene alpha-crystal form nucleating agent
In alkene, crystalling propylene peak temperature, transparency and rigidity (tensile strength and bending modulus) can be effectively improved.With blank
Polypropylene is compared, and Crystallization peak temperature improves 5 DEG C, and mist degree reduces 21.3%, and tensile strength and bending modulus are respectively increased
7.4% and 10.2%.But the aluminum benzoate of fabricated in situ mentions polypropylene transparent and rigid in process
High-amplitude is bigger, and nucleation efficiencies are higher.With blank polypropylene ratio, Crystallization peak temperature improves 7.2 DEG C, and mist degree reduces
44.4%, 11.2% and 21.0% has been respectively increased in tensile strength and bending modulus.Aluminum benzoate and processing are directly added in comparison
In the process the effect of fabricated in situ aluminum benzoate can be seen that the aluminum benzoate of fabricated in situ in process nucleating effect it is bright
The aobvious aluminum benzoate for being better than directly adding.
Embodiment 2
Beta crystal-type nucleater adipic acid zinc being prepared in situ and adding isotactic homopolypropylene
2.9 g of adipic acid (molecular weight: 146) (molecular weight: 81) are uniformly mixed in mortar, so with 1.6 grams of zinc oxide
Afterwards with 1 gram of antioxidant 1010 and 1 gram of irgasfos 168,1000 grams of isotactic polypropylene (Yangtze petrochemical industry, trade mark F401) powders in height
It is uniformly mixed in mixed machine, this mixture is added in double screw extruder and is squeezed out (see Table 1 for details for procession parameters), made
It is standby to obtain the polypropylene resin composite containing adipic acid zinc beta crystal-type nucleater, then it is molded (see Table 2 for details for molding proces s parameters)
At standard batten (ASTM standard), test can be carried out to polyacrylic impact resistance.
Comparative example 2
Simultaneously as a comparison, 4.2 g of adipic acid zinc are added to progress twin-screw in polypropylene directly as nucleating agent to squeeze
Out, remaining prepares the polypropylene resin composite containing adipic acid zinc with embodiment 2.
It can be carried out test using impact resistance of the shock machine to polypropene composition, impact property presses ASTMD256-
2006 standards are tested.Using differential scanning calorimeter (DSC) to the Crystallization peak temperature of this polypropylene resin composite into
Row characterization (DSC temperature rate is 10 DEG C/min)；Divide using beta-crystalline form content of the X-ray diffraction to polypropene composition
Analysis (test sample after thermal station hot pressing in 125 DEG C of isothermal crystals 30 minutes), concrete outcome is as shown in Fig. 2 and table 4.
According to X-ray diffraction principle it is found that different crystalline structures, the position for causing crystalline high polymer characteristic diffraction peak to occur
Difference is set, it is possible thereby to judge which kind of crystal form PP belongs to, and containing for various crystal forms can be calculated according to the height of diffraction maximum
Amount.In 6-25 ° of 2 θ diffraction angular regions, 5 main diffraction peaks of alpha-crystal form, be located at 14.1 °, 16.8 °, 18.6 °,
At 21.2 ° and 21.8 °, it is corresponding in turn to spreading out for crystal faces generations such as (110), (040), (130) and overlapping (131) and (111)
Peak is penetrated, this is the diffraction maximum feature of typical alpha-crystal form polypropylene.Beta crystal is typical beta crystal feature occur at 16.08 ° in 2 θ
(300) crystallographic plane diffraction peak.
According to Turner-Jon formula (formula 1), the relative amount (k value) of beta crystal can be calculated:
K=H (300)/× 100% (1) [H (300)+H (110)+H (040)+H (130)]
H (300) is the peak height in β crystalline substance peak face (300) in formula, and H (110), H (040) and H (130) are respectively the peak face of α crystalline substance
(110), the peak height of (040) and (130).
Table 4
As can be seen from Table 4, adipic acid zinc is added directly into poly- third as effective polypropylene beta crystal nucleating agent
In alkene, polyacrylic Crystallization peak temperature, beta-crystalline form content and toughness (impact strength) can be effectively improved.With blank
Polypropylene is compared, and Crystallization peak temperature improves 6.6 DEG C, and beta-crystalline form content 0.64, impact strength improves 76%.But
The adipic acid zinc of fabricated in situ is for crystalling propylene peak temperature, beta-crystalline form content and impact strength in process
Increase rate is bigger, and nucleation efficiencies are higher.With blank polypropylene ratio, Crystallization peak temperature improves 11 DEG C, and beta-crystalline form content is
0.97, impact strength improves 232%.Original position synthesizing adipic acid zinc in adipic acid zinc and process is directly added in comparison
The nucleating effect that effect can be seen that the adipic acid zinc of fabricated in situ in process is substantially better than directly addition adipic acid zinc.
Embodiment 3
It alpha-crystal form nucleating agent aluminum benzoate being prepared in situ in isotactic homopolypropylene and adds, and and nanoclay
It is compound:
3.6 grams of benzoic acid (molecular weight 123) are uniformly mixed with 1 gram of aluminium oxide (molecular weight 102), then with 1 gram of antioxygen
Agent 1010 and 1 gram irgasfos 168,50 grams of nanoclays (trade names 1.44P, Nanocor company, the U.S.), 1000 grams of isotactics
Polypropylene (Yangtze petrochemical industry, trade mark F401) powder is uniform in high-speed mixer and mixing, this mixture is added to twin-screw extrusion
(see Table 1 for details for extrusion process) is squeezed out in machine, and the acrylic resin combination containing aluminum benzoate alpha-crystal form nucleating agent is prepared
Then object is molded (see Table 2 for details for Shooting Technique) at standard batten (ASTM standard), carries out to polyacrylic stretching and bending property
Test.
Comparative example 3
Simultaneously as a comparison, 4.7 grams of aluminum benzoates are added to progress pair in 1000 grams of polypropylene directly as nucleating agent
Screw Extrusion, remaining prepares the polypropylene resin composite containing aluminum benzoate with embodiment 3.
It is tested using tensile property and bending property of the tensilon to polypropene composition, using impact test
Machine tests shock resistance.Tensile property is tested by ASTM D638-2003, rate of extension 20mm/min；It is curved
Qu Xingneng is tested by ASTM D790-2003, and bending rate is 10mm/min；Impact property by ASTM D256-2006 into
Row test；(DSC liter is characterized to the Crystallization peak temperature of polypropylene resin composite using differential scanning calorimeter (DSC)
Rate of temperature fall 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 is added directly into polypropylene as effective polypropylene alpha-crystal form nucleating agent
In and be used in combination with nanoclay, can effectively improve crystalling propylene peak temperature, rigidity (tensile strength and curved
Bent modulus) and toughness (impact strength).Compared with blank polypropylene, Crystallization peak temperature improves 5.4 DEG C, tensile strength and
7.2% and 19.8% has been respectively increased in bending modulus, and impact strength improves 18.4%.But conjunction in situ in process
At aluminum benzoate and nanoclay it is compound after for polyacrylic Crystallization peak temperature, rigidity and toughness increase rate more
Greatly, nucleation efficiencies are higher.With blank polypropylene ratio, Crystallization peak temperature improves 8 DEG C, and tensile strength and bending modulus mention respectively
High by 12.5% and 31.2%, impact strength improves 26.3%.Aluminum benzoate and process Central Plains are directly added in comparison
The effect compound with nanoclay can be seen that the aluminum benzoate of fabricated in situ in process to position synthesizing benzoic acids aluminium respectively
Nucleating effect is substantially better than the aluminum benzoate directly added.
Embodiment 4
It beta crystal-type nucleater adipic acid zinc being prepared in situ in copolymer polypropylene and adds
2.9 g of adipic acid (molecular weight: 146) (molecular weight: 81) are uniformly mixed in mortar, so with 1.6 grams of zinc oxide
Afterwards with 1 gram of antioxidant 1010 and 1 gram of irgasfos 168,1000 grams of copolymer polypropylene powders (Yangtze petrochemical industry, trade mark C180) in height
It is uniformly mixed in mixed machine, this mixture is added in double screw extruder and is squeezed out (see Table 1 for details for extrusion process), is prepared into
To the polypropylene resin composite containing adipic acid zinc beta crystal-type nucleater, (see Table 2 for details for Shooting Technique) is then molded into standard sample
Item (ASTM standard) can be carried out test to polyacrylic impact resistance.
Comparative example 4
Simultaneously as a comparison, 4.2 g of adipic acid zinc are added to progress twin-screw in polypropylene directly as nucleating agent to squeeze
Out, remaining prepares the polypropylene resin composite containing adipic acid zinc with embodiment 4.
It can be carried out test impact property by ASTM D256- using impact resistance of the shock machine to polypropene composition
2006 are tested；Table is carried out using Crystallization peak temperature of the differential scanning calorimeter (DSC) to this polypropylene resin composite
Sign (DSC temperature rate is 10 DEG C/min)；It is analyzed and (is surveyed using beta-crystalline form content of the X-ray diffraction to polypropene composition
Test agent is after thermal station hot pressing in 125 DEG C of isothermal crystals 30 minutes), concrete outcome is as shown in Fig. 4 and table 6.
Table 6
As can be seen from Table 6, adipic acid zinc directly can be mentioned effectively after addition as effective beta crystal-type nucleater
Crystallization peak temperature, beta-crystalline form content and the toughness (impact strength) of high copolymer polypropylene.With blank copolymer polypropylene phase
Than Crystallization peak temperature improves 3.8 DEG C, and beta-crystalline form content 0.81, impact strength improves 67%.But processed
The adipic acid zinc of fabricated in situ is for crystalling propylene peak temperature, beta-crystalline form content and impact strength increase rate in journey
Bigger, nucleation efficiencies are higher.With blank copolymer polypropylene ratio, Crystallization peak temperature improves 6.6 DEG C, beta-crystalline form content 0.92,
Impact strength improves 105%.The effect of original position synthesizing adipic acid zinc in adipic acid zinc and process is directly added in comparison
As can be seen that the nucleating effect of the adipic acid zinc of fabricated in situ is substantially better than directly addition adipic acid zinc in process.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent defines.
Claims (4)
1. a kind of preparation method of crystalline polypropylene resin composition, comprising:
(1) by 2.9 g of adipic acid of reaction monomers, molecular weight: 146, and 1.6 grams of zinc oxide of metal oxide, molecular weight: 81, it grinds
Mill mixing, is then uniformly mixed in high mixer with 1 gram of antioxidant 1010 and 1 gram of irgasfos 168,1000 grams of isotactic polypropylene powders
It closes；
(2) a. squeezes out mixed isotactic polypropylene resin on screw extruder, and polypropylene resin composite is made；Or b.
Mixed acrylic resin is molded, is blow molded, compression moulding, rotational moulding, slush moulding or extrusion molding, polypropylene resin composite is made.
2. a kind of preparation method of crystalline polypropylene resin composition according to claim 1, it is characterised in that: the step
Suddenly (1) further includes being added selected from one or more of processing aid, filler.
3. a kind of preparation method of crystalline polypropylene resin composition according to claim 2, it is characterised in that: described to fill out
Material is one or more of nanoclay, calcium carbonate, talcum powder.
4. a kind of preparation method of crystalline polypropylene resin composition according to claim 1, it is characterised in that: the step
Suddenly the extrusion temperature of the screw extruder in (2) a is 180-250 DEG C, and screw speed is 50-500 revs/min.
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| 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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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