CN102040772A - Method for regulating mechanical property of polypropylene based on alpha/beta complex nucleating agent - Google Patents
Method for regulating mechanical property of polypropylene based on alpha/beta complex nucleating agent Download PDFInfo
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- CN102040772A CN102040772A CN 201010574151 CN201010574151A CN102040772A CN 102040772 A CN102040772 A CN 102040772A CN 201010574151 CN201010574151 CN 201010574151 CN 201010574151 A CN201010574151 A CN 201010574151A CN 102040772 A CN102040772 A CN 102040772A
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Abstract
The invention relates to a method for regulating mechanical property of polypropylene based on alpha/beta complex nucleating agent, in the method, a polypropylene alpha crystal form nucleating agent and a beta crystal form nucleating agent are in complex use, and a new method for finding out optimal complex proportion of the alpha crystal form nucleating agent and the beta crystal form nucleating agent when total addition concentration is certain is provided; namely, difference delta TC alpha beta between the two nucleating agents at each complex proportion delta TCp is calculated, and the proportion in which the two agents have minimum difference is considered as the optimal complex proportion of the addition concentration. The method has the following advantages: when the two crystal forms of polypropylene nucleating agents are added compositely according to the optimal proportion, tensile strength, flexural modulus and impulse strength of the polypropylene can be simultaneously improved. The optimal proportion of any two nucleating agents under a condition that the total addition concentration is certain can be found out through the calculation method, and processing test on each compound proportion is avoided.
Description
[technical field]
The present invention relates to the polypropylene technology field, specifically, is a kind of method based on α/β composite nucleating agent regulation and control polypropylene mechanical property.
[background technology]
Polypropylene as the interchangeable heat plastic resin have that relative density is low, nontoxic, thermotolerance, erosion resistance, electrical insulating property is good, heat-drawn wire is high, easily processing and advantage such as inexpensive, be widely used in numerous areas, and constantly expanded new application.
Isotatic polypropylene is to belong to semi-crystalline resins, and its known crystal habit has α, β, γ, δ and plan six sides totally 5 kinds of crystallographic systems.Wherein, alpha-crystal form is an oblique crystal, and is the most stable, but there is the relatively poor shortcoming of toughness in it.Therefore, the affiliation that adds of polypropylene alpha-crystal form nucleator significantly promotes polyacrylic stretching and bending property, but its shock strength can slightly descend.Beta crystal belongs to hexagonal system, and the polypropylene of this crystal formation has good impelling strength, but rigidity descends obviously compared to alpha-crystal form polypropylene.Often polypropylene is after adding beta crystal-type nucleater, and shock strength can be greatly enhanced, but tensile property and the bending property of this moment can descend to some extent.From over-all properties consider how to improve polyacrylic rigidity and toughness simultaneously and become a key issue.
Therefore, consider to solve this problem, can improve rigidity and can promote the flexible purpose again in the hope of reaching by the compound use of polypropylene nucleater with α, two kinds of different crystal forms of β.
[summary of the invention]
The objective of the invention is to overcome the deficiencies in the prior art, a kind of method based on α/β composite nucleating agent regulation and control polypropylene mechanical property is provided.
The objective of the invention is to be achieved through the following technical solutions:
A kind of method based on α/β composite nucleating agent regulation and control polypropylene mechanical property with polypropylene alpha-crystal form nucleator and the compound use of beta crystal-type nucleater, is added concentration one regularly total, calculates two kinds of nucleators at the Δ T of each compositely proportional place
CpBetween difference DELTA T
C α β, get the best complex ratio of its minimum place for this interpolation concentration, formula is,
T
C α β=T
CP α-T
CP βFormula 1
Min (| T
C α β|) formula 2
Δ T in the formula 1
Cp α, Δ T
Cp βWhen representing two kinds of nucleators to add separately corresponding concentration, the amplitude that the crystalling propylene peak temperature improves;
Its concrete steps are,
(1) selects a kind of polypropylene alpha-crystal form nucleator, a kind of polypropylene beta crystal nucleating agent; The interpolation concentration of testing both respectively is designated as Δ Δ T respectively for the crystalling propylene Temperature Influence
Cp α, Δ T
Cp β
Described polypropylene alpha-crystal form nucleator comprises that in mineral-type, glucitols, (replacement) aryl carboxylic acid and metallic salt thereof, (replacement) aryl-heterocyclic phosphoric acid salt, the rosin based nucleator one or several are with arbitrary proportion blended nucleator;
Polypropylene beta crystal nucleating agent comprise mineral-type (inorganic salt, metal oxide), condensed-nuclei aromatics class, organic acid and its esters, amides, rare earth organic compounds class nucleator one or several with arbitrary proportion blended nucleator;
(2) always add under the certain condition of concentration at composite nucleating agent, add the pairing Δ T of concentration separately according to two kinds of nucleators
Cp, calculate difference between the two under each compositely proportional, be designated as Δ T
C α β, select Δ T
C α βThe ratio of absolute value minimum is this total optimum proportion that adds under the concentration;
It is 0.005～10% of polypropylene gross weight that composite nucleating agent always adds concentration; Composite nucleating agent is polypropylene alpha-crystal form nucleator and polypropylene beta crystal nucleating agent;
The shared ratio of polypropylene alpha-crystal form nucleator in the composite nucleating agent is 0.5～99.5wt%, and the shared ratio of polypropylene beta crystal nucleating agent is 99.5～0.5wt%;
(3) ratio that two kinds of nucleators will selecting draw according to step (2) is mixed the back and is added polypropylene;
Composite nucleating agent of the present invention can with other materials such as oxidation inhibitor, processing aid, fillers etc. mix to use.
Compared with prior art, positively effect of the present invention is:
(1) polypropylene nucleater of α, two kinds of different crystal forms of β can improve polyacrylic tensile strength, modulus in flexure and shock strength simultaneously with the compound adding polypropylene of optimum proportion;
(2) by calculating any two kinds polypropylene nucleater Δ T
CpBetween difference, select Δ T
C α βThe ratio of absolute value minimum can be found out both at total optimum proportion that adds under the certain condition of concentration, has avoided by each compound proportion is processed test.
[description of drawings]
Fig. 1 polypropylene T
CpAdd the variation diagram of concentration with NA40;
Fig. 2 polypropylene T
CpAdd the variation diagram of concentration with PA-03;
Fig. 3 polypropylene T
CpAdd the variation diagram of concentration with NABW;
Fig. 4 polypropylene T
CpAdd the variation diagram of concentration with S20;
Fig. 5 polypropylene T
CpAdd the variation diagram of concentration with HHPA-Ba.
[embodiment]
The present invention below is provided a kind of embodiment of regulating and control the method for polypropylene mechanical property based on α/β composite nucleating agent.
Embodiment 1
(1) selects a kind of polypropylene alpha-crystal form nucleator NA40, a kind of polypropylene beta crystal nucleating agent PA-03; The interpolation concentration of testing both respectively is designated as Δ T for the crystalling propylene Temperature Influence
CpSee Fig. 1, Fig. 2;
(2) always add concentration when being 0.2wt% at two kinds of nucleators, add the pairing Δ T of concentration separately according to two kinds of nucleators
Cp, calculate difference between the two under each compositely proportional, be designated as Δ T
C α β, select T
C α βThe ratio of absolute value minimum, NA40: PA-03=3: 7 (mass ratioes) are the optimum proportions of two kinds of nucleators when total interpolation concentration is 0.2wt%.
The Δ T of NA40/PA-03 in polypropylene of different proportionings when table 1 interpolation total concn is 0.2wt%
C α βRelatively
(3) 0.6g NA40 is mixed with 1.4g PA-03, add the 1000g polypropylene.
(1) select a kind of polypropylene alpha-crystal form nucleator NA40, a kind of polypropylene beta crystal nucleating agent NABW, the interpolation concentration of testing both respectively is designated as Δ T for the crystalling propylene Temperature Influence
CpSee Fig. 1, Fig. 3;
(2) always add concentration when being 0.2wt% at two kinds of nucleators, add the pairing Δ T of concentration separately according to two kinds of nucleators
Cp, calculate difference between the two under each compositely proportional, be designated as Δ T
C α β, select Δ T
C α βThe ratio of absolute value minimum, NA40: NABW=1: 3 (mass ratioes) are the optimum proportions of two kinds of nucleators when total interpolation concentration is 0.2wt%.
The Δ T of NA40/NABW in polypropylene of different proportionings when table 2 interpolation total concn is 0.2wt%
C α βRelatively
(3) 0.5g NA40 is mixed with 1.5g NABW, add the 1000g polypropylene.
Embodiment 3
(1) selects a kind of polypropylene alpha-crystal form nucleator S20, a kind of polypropylene beta crystal nucleating agent PA-03.The interpolation concentration of testing both respectively is designated as Δ T for the crystalling propylene Temperature Influence
Cp, see Fig. 4, Fig. 2;
(2) always add concentration when being 0.3wt% at two kinds of nucleators, add the pairing Δ T of concentration separately according to two kinds of nucleators
Cp, calculate difference between the two under each compositely proportional, be designated as Δ T
C α β, select Δ T
C α βThe ratio of absolute value minimum, S20: PA-03=2: 3 (mass ratioes) are the optimum proportions of two kinds of nucleators when total interpolation concentration is 0.3wt%;
The Δ T of S20/PA-03 in polypropylene of different proportionings when table 3 interpolation total concn is 0.3wt%
C α βRelatively
(3) 1.2g S20 is mixed with 1.8g PA-03, add the 1000g polypropylene.
(1) select a kind of polypropylene alpha-crystal form nucleator S20, a kind of polypropylene beta crystal nucleating agent HHPa-Ba, the interpolation concentration of testing both respectively is designated as Δ T for the crystalling propylene Temperature Influence
CpSee Fig. 4, Fig. 5;
(2) always add concentration when being 0.3wt% at two kinds of nucleators, add the pairing Δ T of concentration separately according to two kinds of nucleators
Cp, calculate difference between the two under each compositely proportional, be designated as Δ T
C α β, select Δ T
C α βThe ratio of absolute value minimum, S20: HHPa-Ba=1: 2 (mass ratioes) are the optimum proportions of two kinds of nucleators when total interpolation concentration is 0.3wt%;
The Δ T of S20/HHPa-Ba in polypropylene of different proportionings when table 4 interpolation total concn is 0.3wt%
C α βRelatively
(3) 1g S20 is mixed with 2g HHPa-Ba, add the 1000g polypropylene.
Embodiment 5
Below by example use of the present invention is further specified.
Be mixed with the polypropylene (trade mark: T30S) carry out extruding pelletization of nucleator by the SJSH twin screw extruder.Open wide to place and removed moisture in 48 hours, make the polypropylene batten by the CJ-80E injection moulding machine then.After batten is at room temperature placed 24 hours, carry out Mechanics Performance Testing, shock strength is tested according to ASTM D-256; Tensile strength is tested by ASTM D-638-00; Modulus in flexure is tested by ASTM D-790-00.Blank polypropylene is also made batten with same process, as a comparison case, carries out above-mentioned test.
The contrast of table 5 mechanical property
The above only is a preferred implementation of the present invention; should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (5)
1. the method based on α/β composite nucleating agent regulation and control polypropylene mechanical property is characterized in that, with polypropylene alpha-crystal form nucleator and the compound use of beta crystal-type nucleater, adds concentration one regularly total, calculates two kinds of nucleators at the Δ T of each compositely proportional place
CpBetween difference DELTA T
C α β, get the best complex ratio of its minimum place for this interpolation concentration, formula is,
T
C α β=T
CP α-T
CP βFormula 1
Min (| T
C α β|) formula 2
Δ T in the formula 1
Cp α, Δ T
Cp βWhen representing two kinds of nucleators to add separately corresponding concentration, the amplitude that the crystalling propylene peak temperature improves;
Its concrete steps are,
(1) selects a kind of polypropylene alpha-crystal form nucleator, a kind of polypropylene beta crystal nucleating agent; The interpolation concentration of testing both respectively is designated as Δ T respectively for the crystalling propylene Temperature Influence
Cp α, Δ T
Cp β
(2) always add under the certain condition of concentration at composite nucleating agent, add the pairing Δ T of concentration separately according to two kinds of nucleators
Cp, calculate difference between the two under each compositely proportional, be designated as Δ T
C α β, select Δ T
C α βThe ratio of absolute value minimum is this total optimum proportion that adds under the concentration;
(3) ratio that two kinds of nucleators will selecting draw according to step (2) is mixed the back and is added polypropylene.
2. a kind of method as claimed in claim 1 based on α/β composite nucleating agent regulation and control polypropylene mechanical property, it is characterized in that described polypropylene alpha-crystal form nucleator comprises that in mineral-type, glucitols, (replacement) aryl carboxylic acid and metallic salt thereof, (replacement) aryl-heterocyclic phosphoric acid salt, the rosin based nucleator one or several are with arbitrary proportion blended nucleator.
3. a kind of method as claimed in claim 1 based on α/β composite nucleating agent regulation and control polypropylene mechanical property, it is characterized in that, described polypropylene beta crystal nucleating agent comprise mineral-type (inorganic salt, metal oxide), condensed-nuclei aromatics class, organic acid and its esters, amides, rare earth organic compounds class nucleator one or several with arbitrary proportion blended nucleator.
4. a kind of method based on α/β composite nucleating agent regulation and control polypropylene mechanical property as claimed in claim 1 is characterized in that it is 0.005～10% of polypropylene gross weight that described composite nucleating agent always adds concentration; Composite nucleating agent is polypropylene alpha-crystal form nucleator and polypropylene beta crystal nucleating agent.
5. a kind of method as claimed in claim 1 based on α/β composite nucleating agent regulation and control polypropylene mechanical property, it is characterized in that, the shared ratio of polypropylene alpha-crystal form nucleator in the described composite nucleating agent is 0.5～99.5wt%, and the shared ratio of polypropylene beta crystal nucleating agent is 99.5～0.5wt%.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610695A (en) * | 2015-01-15 | 2015-05-13 | 佛山顾地塑胶有限公司 | Preparation method of modifying master batch for PP (polypropylene) structured wall pipes |
| CN105153556A (en) * | 2015-07-30 | 2015-12-16 | 苏州润佳工程塑料股份有限公司 | High-performance polypropylene material and preparation method thereof |
| CN105385032A (en) * | 2015-12-14 | 2016-03-09 | 上海金发科技发展有限公司 | Isotropous polypropylene compound and preparation method thereof |
| CN107254101A (en) * | 2017-06-20 | 2017-10-17 | 苏州旭光聚合物有限公司 | Handle of automobile roof modified polypropene |
| CN107793635A (en) * | 2016-08-30 | 2018-03-13 | 李长荣化学工业股份有限公司 | Polypropylene expanded body and preparation method thereof |
| CN108384062A (en) * | 2018-03-19 | 2018-08-10 | 盐城科迈特新材料有限公司 | Rigid toughening nucleating agent of a kind of polypropylene increasing and preparation method thereof |
| CN112028929A (en) * | 2019-06-03 | 2020-12-04 | 华东理工大学 | Preparation method and application of polyhedral oligomeric silsesquioxane-loaded substituted aryl heterocyclic phosphate or salt nucleating agent |
| CN112143116A (en) * | 2020-09-27 | 2020-12-29 | 上海金发科技发展有限公司 | Polypropylene composite material with consistent crystallinity of skin layer and core layer and preparation method thereof |
| CN115785523A (en) * | 2021-09-13 | 2023-03-14 | 华东理工大学 | Composition and application of alpha/beta composite nucleating agent for regulating and controlling mechanical property of polypropylene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6005034A (en) * | 1995-08-31 | 1999-12-21 | Chisso Corpoation | Propylene-ethylene copolymer composition and process for producing the same |
| CN101503539A (en) * | 2009-02-26 | 2009-08-12 | 浙江富丽新材料有限公司 | Toughened cold-resistant transparent modified polypropylene material and preparation |
| WO2010037747A1 (en) * | 2008-10-01 | 2010-04-08 | Borealis Ag | New sewage pipe material with improved properties |
-
2010
- 2010-12-06 CN CN201010574151XA patent/CN102040772B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6005034A (en) * | 1995-08-31 | 1999-12-21 | Chisso Corpoation | Propylene-ethylene copolymer composition and process for producing the same |
| WO2010037747A1 (en) * | 2008-10-01 | 2010-04-08 | Borealis Ag | New sewage pipe material with improved properties |
| CN101503539A (en) * | 2009-02-26 | 2009-08-12 | 浙江富丽新材料有限公司 | Toughened cold-resistant transparent modified polypropylene material and preparation |
Non-Patent Citations (2)
| Title |
|---|
| 《Journal of Polymer Science: Patt B: Polymer Physics》 20100315 SHICHENG ZHAO，et al. Nucleation Characteristics of the alpha/beta Compounded Nucleating Agents and Their Influences on Crystallization Behavior and Mechanical Properties of Isotactic Polypropylene 653-665 1-5 第48卷, 第6期 2 * |
| 《国外塑料》 20071031 辛忠 基于成核剂的聚丙烯结晶过程调控技术与理论 65-81 1-5 第25卷, 第10期 2 * |
Cited By (12)
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| CN104610695A (en) * | 2015-01-15 | 2015-05-13 | 佛山顾地塑胶有限公司 | Preparation method of modifying master batch for PP (polypropylene) structured wall pipes |
| CN104610695B (en) * | 2015-01-15 | 2017-06-16 | 佛山顾地塑胶有限公司 | A kind of preparation method of Polypropylene structural wall pipe modified master |
| CN105153556A (en) * | 2015-07-30 | 2015-12-16 | 苏州润佳工程塑料股份有限公司 | High-performance polypropylene material and preparation method thereof |
| CN105385032A (en) * | 2015-12-14 | 2016-03-09 | 上海金发科技发展有限公司 | Isotropous polypropylene compound and preparation method thereof |
| CN107793635A (en) * | 2016-08-30 | 2018-03-13 | 李长荣化学工业股份有限公司 | Polypropylene expanded body and preparation method thereof |
| US10882968B2 (en) | 2016-08-30 | 2021-01-05 | Lcy Chemical Corporation | Polypropylene foams and processes of making |
| CN107254101A (en) * | 2017-06-20 | 2017-10-17 | 苏州旭光聚合物有限公司 | Handle of automobile roof modified polypropene |
| CN108384062A (en) * | 2018-03-19 | 2018-08-10 | 盐城科迈特新材料有限公司 | Rigid toughening nucleating agent of a kind of polypropylene increasing and preparation method thereof |
| CN112028929A (en) * | 2019-06-03 | 2020-12-04 | 华东理工大学 | Preparation method and application of polyhedral oligomeric silsesquioxane-loaded substituted aryl heterocyclic phosphate or salt nucleating agent |
| CN112143116A (en) * | 2020-09-27 | 2020-12-29 | 上海金发科技发展有限公司 | Polypropylene composite material with consistent crystallinity of skin layer and core layer and preparation method thereof |
| CN115785523A (en) * | 2021-09-13 | 2023-03-14 | 华东理工大学 | Composition and application of alpha/beta composite nucleating agent for regulating and controlling mechanical property of polypropylene |
| CN115785523B (en) * | 2021-09-13 | 2023-10-10 | 华东理工大学 | Composition and application of alpha/beta composite nucleating agent for regulating and controlling mechanical properties of polypropylene |
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