CN102040772B - 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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- CN102040772B CN102040772B CN201010574151XA CN201010574151A CN102040772B CN 102040772 B CN102040772 B CN 102040772B CN 201010574151X A CN201010574151X A CN 201010574151XA CN 201010574151 A CN201010574151 A CN 201010574151A CN 102040772 B CN102040772 B CN 102040772B
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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 Vestolen PP 7052 mechanical property.
[background technology]
Vestolen PP 7052 as the interchangeable heat plastic resin have that specific density is low, nontoxic, thermotolerance, erosion resistance, electrical insulating property is good, heat-drawn wire is high, be prone to 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 Vestolen PP 7052 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 Vestolen PP 7052 of this crystal formation has good impelling strength, but rigidity descends obviously compared to alpha-crystal form polypropylene.Often Vestolen PP 7052 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 through 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 deficiency of prior art, a kind of method based on α/β composite nucleating agent regulation and control Vestolen PP 7052 mechanical property is provided.
The objective of the invention is to realize through following technical scheme:
A kind of method based on α/β composite nucleating agent regulation and control Vestolen PP 7052 mechanical property with Vestolen PP 7052 alpha-crystal form nucleator and the compound use of beta crystal-type nucleater, is added concentration one timing total, calculate two kinds of nucleators at each compositely proportional place Δ T
CpBetween difference DELTA T
C α β, get the best complex ratio of its minimum place for this interpolation concentration, formula does,
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 do,
(1) selects a kind of Vestolen PP 7052 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 Influence of Temperature
Cp α, Δ T
Cp β
Described Vestolen PP 7052 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, MOX), 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 minimum ratio of absolute value is this total optimum proportion that adds under the concentration;
It is 0.005～10% of Vestolen PP 7052 gross weight that composite nucleating agent always adds concentration; Composite nucleating agent is Vestolen PP 7052 alpha-crystal form nucleator and polypropylene beta crystal nucleating agent;
The shared ratio of Vestolen PP 7052 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 Vestolen PP 7052;
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 Vestolen PP 7052 of optimum proportion;
(2) through calculating any two kinds polypropylene nucleater Δ T
CpBetween difference, select Δ T
C α βThe minimum ratio of absolute value can be found out both at total optimum proportion that adds under the certain condition of concentration, has avoided through each compound proportion is processed test.
[description of drawings]
Fig. 1 Vestolen PP 7052 T
CpAdd the variation diagram of concentration with NA40;
Fig. 2 Vestolen PP 7052 T
CpAdd the variation diagram of concentration with PA-03;
Fig. 3 Vestolen PP 7052 T
CpAdd the variation diagram of concentration with NABW;
Fig. 4 Vestolen PP 7052 T
CpAdd the variation diagram of concentration with S20;
Fig. 5 Vestolen PP 7052 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 Vestolen PP 7052 mechanical property based on α/β composite nucleating agent.
Embodiment 1
(1) selects a kind of Vestolen PP 7052 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 Influence of Temperature
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 that absolute value is 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 Vestolen PP 7052 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 Vestolen PP 7052.
(1) select a kind of Vestolen PP 7052 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 Influence of Temperature
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 that absolute value is 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 Vestolen PP 7052 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 Vestolen PP 7052.
Embodiment 3
(1) selects a kind of Vestolen PP 7052 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 Influence of Temperature
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 that absolute value is 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 Vestolen PP 7052 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 Vestolen PP 7052.
(1) select a kind of Vestolen PP 7052 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 Influence of Temperature
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 that absolute value is 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 Vestolen PP 7052 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 Vestolen PP 7052.
Embodiment 5
Below through instance use of the present invention is further specified.
Be mixed with the Vestolen PP 7052 (trade mark: T30S) carry out extruding pelletization of nucleator through the SJSH twin screw extruder.Open wide to place and removed moisture in 48 hours, process the Vestolen PP 7052 batten through 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 Vestolen PP 7052 is also processed batten with same process, and example is carried out above-mentioned test as a comparison.
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, under the prerequisite that does not break away from the present invention's design; Can also make some improvement and retouching, these improvement and retouching also should be regarded as in protection scope of the present invention.
Claims (5)
1. the method based on α/β composite nucleating agent regulation and control Vestolen PP 7052 mechanical property is characterized in that, with Vestolen PP 7052 alpha-crystal form nucleator and the compound use of beta crystal-type nucleater, adds concentration one timing total, calculate two kinds of nucleators at each compositely proportional place Δ T
CpBetween difference DELTA T
C α β, get the best complex ratio of its minimum place for this interpolation concentration, formula does,
Formula 1:
ΔT
Cαβ＝ΔT
Cpα-ΔT
Cpβ
Formula 2:
Min?(|ΔT
Cαβ|)
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 do,
(1) select a kind of Vestolen PP 7052 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 Influence of Temperature
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 minimum ratio of absolute value 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 Vestolen PP 7052.
2. a kind of method as claimed in claim 1 based on α/β composite nucleating agent regulation and control Vestolen PP 7052 mechanical property; It is characterized in that described Vestolen PP 7052 alpha-crystal form nucleator comprises that in mineral-type, glucitols, replacement or unsubstituting aromatic yl carboxylic acid and metallic salt, replacement or unsubstituting aromatic yl heterocycle 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 Vestolen PP 7052 mechanical property; It is characterized in that, described polypropylene beta crystal nucleating agent comprise mineral-type, 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 Vestolen PP 7052 mechanical property as claimed in claim 1 is characterized in that it is 0.005～10% of Vestolen PP 7052 gross weight that described composite nucleating agent always adds concentration; Composite nucleating agent is Vestolen PP 7052 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 Vestolen PP 7052 mechanical property; It is characterized in that; The shared ratio of Vestolen PP 7052 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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| 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 |
| 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 |
| 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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