CN101993565A - High tenacity and high impact polypropylene resin composition - Google Patents

High tenacity and high impact polypropylene resin composition Download PDF

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Publication number
CN101993565A
CN101993565A CN2009100566418A CN200910056641A CN101993565A CN 101993565 A CN101993565 A CN 101993565A CN 2009100566418 A CN2009100566418 A CN 2009100566418A CN 200910056641 A CN200910056641 A CN 200910056641A CN 101993565 A CN101993565 A CN 101993565A
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China
Prior art keywords
nucleator
additive
weight
tenacity
nucleating agent
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Pending
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CN2009100566418A
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Chinese (zh)
Inventor
高道春
钟峰
陆玲芳
徐文俊
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China Petroleum and Chemical Corp
Sinopec Shanghai Petrochemical Co Ltd
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Sinopec Shanghai Petrochemical Co Ltd
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Priority to CN2009100566418A priority Critical patent/CN101993565A/en
Publication of CN101993565A publication Critical patent/CN101993565A/en
Pending legal-status Critical Current

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Abstract

A high tenacity and high impact polypropylene resin composition is prepared by melting, mixing and granulating the base material of the polypropylene resins and an additive, wherein the base material of the polypropylene resins is propylene-ethylene random copolymer; the content of ethylene in the copolymer is 5-20wt%; the melt flow rate is 1-10g/10min; the additive include a nucleating agent A, a nucleating agent B, a lubricating agent and an antioxidant; the nucleating agent A is aromatic amide and the nucleating agent B is ortho dicarboxylic acid salt; the weight ratio of the base material of the polypropylene resins to the additive is 1000:1-10; the weight ratio of the nucleating agent A to the nucleating agent B in the additive is 1:0.2-1; and when the total content of the nucleating agent A and the nucleating agent B is 1 part by weight, the lubricating agent is 2-6 parts by weight and the antioxidant is 1-5 parts by weight. Compared with the prior art, the polypropylene resins provided by the invention have excellent tenacity and obviously improved impact resistance (under normal/low temperature).

Description

High tenacity high impact resistance polypropylene resin combination
Technical field
The present invention relates to the acrylic resin is the composition of base-material, particularly adds the polypropylene resin composite that additives such as nucleator, lubricant and oxidation inhibitor carry out high tenacity and impact modification by melting mixing.
Background technology
Acrylic resin becomes one of general-purpose plastics that is most widely used because of plurality of advantages such as raw material sources are abundant, synthesis technique is simple, cheap, over-all properties is good.Toughness is low, the critical defect of erosion-resisting characteristics difference but acrylic resin exists, introduce in the molecular chain and (be generally 5~20wt%) comonomer ethene and form toughness and the erosion-resisting characteristics that segmented copolymer can obviously improve acrylic resin in right amount, but the method for this chemical modification can be subjected to the restriction of heat-resistant deforming performance variation and rigidity reduction, be it to the raising of acrylic resin toughness and erosion-resisting characteristics be limited, otherwise will cause the reduction of acrylic resin heat-drawn wire, and the variation that causes physicalies such as hardness, flexural strength.
Polypropylene or propylene-ethylene copolymers are hemicrystalline polymkeric substance, difference is that the regularity of propylene-ethylene copolymers is low so that degree of crystallinity is relatively low, both all can form multiple crystalline states such as α, β, γ, δ, usually the crystalline region mainly is made of α and beta crystal, and the ratio of alpha-crystal form is far above beta crystal.The characteristic of Beta-crystalline polyacrylic or propylene-ethylene copolymers is to have good toughness, and physicalies such as elongation at break, notched Izod impact strength obviously are better than alpha-crystal form.The crystallized form that alpha-crystal form is or propylene-ethylene copolymers is the most common and the most stable, and beta crystal is quasi-steady type crystal formation on thermodynamics, belong on the kinetics and be unfavorable for a kind of crystal formation of generating, adopt introduced beta crystal-type nucleater more in the prior art in polymkeric substance, so that bring out the formation beta crystal during its crystallization.The ripe at present beta crystal-type nucleater that uses is also few, mainly contains N, N '-dicyclohexyl-2,6-naphthalene diamide, N, N, N ', N '-amidess such as tetraalkyl terephthalamide.There is the common defective in these existing beta crystal-type nucleaters, (measuring method is the DSC method to contain 70~80% beta crystal in the crystalline region that their multipotencys form polypropylene or polypropylene-ethylene copolymer, be Differential scanning calorimetry), thus not ideal enough to the modification of polypropylene raising toughness and erosion-resisting characteristics.
Summary of the invention
The invention provides a kind of high tenacity high impact resistance polypropylene resin combination, it contains a kind of composite beta crystal-type nucleater, under identical crystallization condition, can make in the crystalline region ratio of beta crystal bring up to (DSC method) more than 85%, can remedy the defective that prior art exists effectively.
Below be the concrete technical scheme of the present invention:
A kind of high tenacity high impact resistance polypropylene resin combination, said composition is made after the melting mixing granulation by acrylic resin base-material and additive.Wherein, the acrylic resin base-material is the propylene-ethylene random copolymers, and its ethylene content is 5~20wt%, and melt flow rate (MFR) is 1~10g/10min; Additive comprises nucleator A, nucleator B, lubricant and oxidation inhibitor.
Nucleator A is the aryl amide compound with following structure:
R, the R ' alkyl of C3~C8 of respectively doing for oneself wherein, Ar is the aromatic amide of following structure:
Nucleator B is the ortho position dicarboxylate with following structure:
Wherein X is monocycle alkyl or the multi-ring alkyl of C3~C8, and M is a kind of in the IIB metallic element;
The weight ratio of acrylic resin base-material and additive is 1000: 1~10;
The weight ratio of nucleator A and nucleator B is 1: 0.2~1 in the additive, and when the total amount of nucleator A and nucleator B was 1 weight part, lubricant was 2~6 weight parts, and oxidation inhibitor is 1~5 weight part.
Above-mentioned lubricant can be selected the mixture of stearin, calcium stearate and erucicamide for use, and when stearin was 1 weight part, calcium stearate was 0.8~1.5 weight part, and erucicamide is 0.8~1.2 weight part.
Above-mentioned oxidation inhibitor can be selected the mixture of antioxidant 1010 and oxidation inhibitor 168 for use, and the weight ratio of antioxidant 1010 and oxidation inhibitor 168 is 1: 0.3~0.6.
The weight ratio of above-mentioned acrylic resin base-material and additive is preferably 1000: 3~and 6; In the additive weight ratio of nucleator A and nucleator B be preferably 1: 0.2~0.6.
Essence of the present invention is to have adopted a kind of new composite beta crystal-type nucleater, the contriver finds by a large amount of experiments, under identical crystallization condition, adopt this nucleator can make the ratio of beta crystal in the propylene-ethylene copolymers crystalline region bring up to (DSC method) more than 85%.Same as the prior art, also added necessary lubricant and the oxidation inhibitor of post-treatment in the resin, lubricant and oxidation inhibitor do not propose special requirement because having adopted new nucleator, they all can use in the prior art lubricant and oxidation inhibitor commonly used, select for use in the above technical scheme only for the present invention's recommendation.
Compared with prior art, acrylic resin provided by the invention has more good toughness, and erosion-resisting characteristics (normal, low temperature) is significantly improved.
Below will the invention will be further described by specific embodiment.
In an embodiment, the testing standard of each rerum natura is respectively:
1) melt flow rate (MFR): GB3682 (230 ℃/2.160kg)
2) stretching yield stress: ASTM D638-2003
3) socle girder notched Izod impact strength (23 ℃ ,-20 ℃): ASTM D256-2006
4) modulus in flexure: ASTM D790-2003
Brilliant Determination on content of β type and characterizing method are in the crystalline region:
Adopt differential scanning calorimeter that sample is carried out fusing point and Tc test, polymkeric substance goes out to represent the fusion endotherm(ic)peak of alpha-crystal form near 165 ℃, go out to represent the endotherm(ic)peak of beta crystal near 150 ℃.T αBe alpha-crystal form fusing point, T βBe the beta crystal fusing point, Δ H αBe the alpha-crystal form melting enthalpy, Δ H βBe the beta crystal melting enthalpy.
Beta crystal relative content X β=Δ H β/ (Δ H α+ Δ H β).
Embodiment
[embodiment 1~6]
With nucleator A in the technique scheme and nucleator B, lubricant stearic acid glyceryl ester, calcium stearate and erucicamide, antioxidant 1010 and oxidation inhibitor 168 measure respectively in the back adding mixing tank and mix homogenizing, and homogenizing drops into extrusion machine and is pressed into the particulate state composite additive after two hours;
Above-mentioned composite additive and acrylic resin base-material are measured the back uniform mixing respectively, drop into twin screw extruder and carry out the melting mixing granulation.The residence time of material in screw rod is 1~4 minute, and extruder temperature is controlled to be 145~210 ℃, and screw speed is controlled to be 100~300 rev/mins.The acrylic resin particle that obtains is finished product behind cooling drying.
The acrylic resin base-material is the propylene-ethylene random copolymers, and its ethylene content is 5~20wt%, and melt flow rate (MFR) is 1~10g/10min.
The proportioning of the proportioning of each embodiment additive, acrylic resin base-material and additive sees Table 1 and table 2, and the product that each embodiment is obtained carries out brilliant Determination on content of β type and sign in physical property measurement, the crystalline region respectively, the results are shown in Table 3.
Table 1. (weight part)
Table 2. (weight part)
Nucleator A+B Lubricant Oxidation inhibitor The acrylic resin base-material Additive
Embodiment 1 1 2 4 1000 1
Embodiment 2 1 5 2 1000 6
Embodiment 3 1 6 1 1000 10
Embodiment 4 1 4 5 1000 5
Embodiment 5 1 5 5 1000 6
Embodiment 6 1 5 3 1000 3
Table 3.

Claims (5)

1. high tenacity high impact resistance polypropylene resin combination, said composition is made after the melting mixing granulation by acrylic resin base-material and additive, and wherein, the acrylic resin base-material is the propylene-ethylene random copolymers, its ethylene content is 5~20wt%, and melt flow rate (MFR) is 1~10g/10min; Additive comprises nucleator A, nucleator B, lubricant and oxidation inhibitor, it is characterized in that:
Nucleator A is the aryl amide compound with following structure:
R, the R ' alkyl of C3~C8 of respectively doing for oneself wherein, Ar is the aromatic amide of following structure:
Nucleator B is the ortho position dicarboxylate with following structure:
Wherein X is monocycle alkyl or the multi-ring alkyl of C3~C8, and M is a kind of in the II B metallic element;
The weight ratio of acrylic resin base-material and additive is 1000: 1~10;
The weight ratio of nucleator A and nucleator B is 1: 0.2~1 in the additive, and when the total amount of nucleator A and nucleator B was 1 weight part, lubricant was 2~6 weight parts, and oxidation inhibitor is 1~5 weight part.
2. high tenacity high impact resistance polypropylene resin combination according to claim 1, it is characterized in that described lubricant is the mixture of stearin, calcium stearate and erucicamide, when stearin is 1 weight part, calcium stearate is 0.8~1.5 weight part, and erucicamide is 0.8~1.2 weight part.
3. high tenacity high impact resistance polypropylene resin combination according to claim 1 is characterized in that described oxidation inhibitor is the mixture of antioxidant 1010 and oxidation inhibitor 168, and the weight ratio of antioxidant 1010 and oxidation inhibitor 168 is 1: 0.3~0.6.
4. high tenacity high impact resistance polypropylene resin combination according to claim 1, the weight ratio that it is characterized in that described acrylic resin base-material and additive is 1000: 3~6.
5. high tenacity high impact resistance polypropylene resin combination according to claim 1 is characterized in that the weight ratio of nucleator A and nucleator B is 1: 0.2~0.6 in the described additive.
CN2009100566418A 2009-08-19 2009-08-19 High tenacity and high impact polypropylene resin composition Pending CN101993565A (en)

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Application Number Priority Date Filing Date Title
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516672A (en) * 2011-11-14 2012-06-27 江苏金发科技新材料有限公司 Beta crystal form ethylene propylene polypropylene random copolymer composite and preparation method thereof
CN103965545A (en) * 2013-01-25 2014-08-06 中国石油化工股份有限公司 Polypropylene beta crystal form nucleating agent composition and preparation method thereof, and beta crystal form polypropylene composition and preparation method thereof
CN104356579A (en) * 2014-10-09 2015-02-18 中国石油化工股份有限公司 High-impact polypropylene bottle cap material and preparation method thereof
CN108410018A (en) * 2018-02-09 2018-08-17 江苏汉光实业股份有限公司 Polypropylene building mould additive and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516672A (en) * 2011-11-14 2012-06-27 江苏金发科技新材料有限公司 Beta crystal form ethylene propylene polypropylene random copolymer composite and preparation method thereof
CN103965545A (en) * 2013-01-25 2014-08-06 中国石油化工股份有限公司 Polypropylene beta crystal form nucleating agent composition and preparation method thereof, and beta crystal form polypropylene composition and preparation method thereof
CN103965545B (en) * 2013-01-25 2016-08-17 中国石油化工股份有限公司 A kind of polypropylene beta crystal form nucleating agent composition and preparation method thereof and a kind of beta-crystal polypropylene composition and preparation method thereof
CN104356579A (en) * 2014-10-09 2015-02-18 中国石油化工股份有限公司 High-impact polypropylene bottle cap material and preparation method thereof
CN108410018A (en) * 2018-02-09 2018-08-17 江苏汉光实业股份有限公司 Polypropylene building mould additive and preparation method thereof

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Application publication date: 20110330