CN102344388B - Polypropylene beta nucleating agent and its preparation method and use - Google Patents
Polypropylene beta nucleating agent and its preparation method and use Download PDFInfo
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Abstract
The invention discloses a polypropylene beta nucleating agent. The polypropylene beta nucleating agent is N,N'-dicyclohexyl-1,5-diamido-2,6-naphthalimide. The invention also provides a preparation method of the polypropylene beta nucleating agent. The polypropylene beta nucleating agent is prepared from a raw material of 10 to 30g of naphthalenedicarboxylic acid by a series of reactions. The polypropylene beta nucleating agent is characterized in that the polypropylene beta nucleating agent has good selectivity and high nucleating efficiency, can induce polypropylene to produce beta crystals with high content, can improve greatly a polypropylene crystallization temperature, and has NH2 functional groups having reaction activity so that the polypropylene beta nucleating agent can undergo a few specific reactions with other substances to further expand beta nucleating agent functions.
Description
Technical field
The present invention relates to a kind of beta nucleater, be specifically related to a kind of polyacrylic beta nucleater, the invention still further relates to preparation method and the application of described beta nucleater.
Background technology
Polypropylene (PP) is one of five large general-purpose plastics, has good processing, mechanics and chemical resistance, has a wide range of applications at aspects such as household electrical appliance, automobile, electronics, packaging and building materials furniture.But PP also has many weak points, particularly poor toughness, and low temperature brittleness is large, limit the further expansion of PP Application Areas.Therefore, PP is carried out to modification and there is important theory significance and wide commercial space.Polypropylene is a kind of heteromorphic polymer, has the crystal formations such as α, β, γ, δ and plan hexagonal crystal, and wherein beta crystal density is lower, short texture, while being subject to External Force Acting, easily produce viscous deformation, form micro-crazing or micropore, thereby be conducive to the toughness of dissipation of energy raising PP.Therefore, in the molding process of PP, manage the generation of a large amount of β crystalline substances in induction system, can reach the object of Toughened PP.
Beta nucleater is to induce PP to produce a class material of high-content β crystalline substance.Beta nucleater is divided into organic and inorganic two large classes.Organic mainly contains condensed-nuclei aromatics class (dye class), amides, organic acid and salt.Mineral-type mainly contains inorganic salts, inorganic oxide and some metal powder with low melting points.The beta nucleater of producing for commercialization is the earliest aromatic amine nucleator.This type of beta nucleater is applied for a patent in 1992 by new physics and chemistry company of Japan, and has realized commercialization in 1998.Common aromatic amine nucleator mainly contains two kinds: 2,6-phthalic acid Cyclohexamide (DCTH) [EP 0557721] and N, N '-dicyclohexyl-2,6-aphthalimide (DCNDCA, trade(brand)name NJStar, NJS or NU-100) [EP 0865909A1].In recent years, Shanxi chemical research institute of China develops the beta nucleater that trade names are TMB-4 and TMB-5, is substituted aromatic amide, also belongs to this type of.CN85100465 and CN101605749A etc. disclose a series of (particularly pimelic acid and calcium stearate) beta nucleaters that are made up of the salt of di-carboxylic acid and periodictable ZhongⅡ A family metallic element.CN00117339 discloses rare earth organic complex WBG as polypropylene beta nucleator.
In order to reduce costs and improve the nucleation efficiency of beta nucleater, first CN101157771B and CN101580601A disclose di-carboxylic acid have been carried out to load, and then prepare the method for beta nucleater.CN101619143B discloses a kind of fiber-loaded beta nucleating agent, can utilize the enhancement function of filamentary material and the excellent toughness of β crystalline substance, makes the polypropylene composite material of preparation when strength and modulus does not reduce, obviously improves toughness and the ductility of material.Above-mentioned loading type beta nucleater is all the expanded application about the beta nucleater of organic acid and salt.For other class beta nucleater, owing to lacking the active group that can react in its structure, its further modification application is restricted.
Summary of the invention
The object of the present invention is to provide a kind of selectivity and the higher beta nucleater of nucleation efficiency.
Beta nucleater of the present invention is N, N '-dicyclohexyl-1,5-diamino-2,6-aphthalimide.Its structural formula is as follows:
This beta nucleater can improve polypropylene beta crystal content, improves crystalling propylene temperature, thereby reaches the object of improving Properties of Polypropylene.Simultaneously in its structure with have reactive behavior-NH
2functional group, can carry out some with other materials and specifically react, and further expands the function of this beta nucleater.
Another object of the present invention is to provide the preparation method of described beta nucleater.
The preparation method of beta nucleater provided by the invention is as follows:
(1) in 100～300ml acid with strong oxidizing property, add 10～30g naphthalene dicarboxylic acids, by mixed solution heated and stirred, controlling temperature of reaction is 50～100 DEG C, and reaction times 10～24h carries out the dry intermediate product NA-1 that obtains of suction filtration to reaction solution afterwards;
(2) 1～5g NA-1 is dissolved in 10～30ml organic solvent, add the catalyzer of 0～0.1g, then the acyl chlorides agent sulfur oxychloride that to add with NA-1 mol ratio be 1:1～5:1, controlling temperature of reaction is 50～100 DEG C, reaction times 10～24h, afterwards to the dry intermediate product NA-2 that obtains of reaction solution suction filtration;
(3) hexahydroaniline that is 1:1～3:1 by mol ratio and triethylamine join in 10～50ml organic solvent, 1～5g NA-2 is dissolved in and in identical organic solvent, forms 5～20ml solution, these two kinds of solution are mixed, at 5～50 DEG C, stir 1～5h, afterwards the dry intermediate product obtaining of reaction solution suction filtration is to NA-3;
(4) after adding the catalyzer of 0.5～1.5g in the 50ml organic solution that contains 1～5g NA-3, at 20～50 DEG C, stir 10～24h, mixed solution is dry by 300～500ml dimethyl sulfoxide (DMSO) filtering and washing again, finally obtain tan solid and be target product NA, be i.e. polypropylene beta nucleator.
Further scheme is: the step (1) in above-mentioned preparation method, described acid with strong oxidizing property is concentrated nitric acid, and before suction filtration, reaction solution need to dilute in frozen water.
Further scheme is: the step (2) in above-mentioned preparation method, and described organic solvent is 1,2-ethylene dichloride, described catalyzer is pyridine, dimethyl formamide DMF or benzyltriethylammoinium chloride.
Further scheme is: the step (3) in above-mentioned preparation method, described organic solvent is methylene dichloride, and hexahydroaniline and triethylamine are joined in appropriate methylene dichloride, then the dichloromethane solution that is dissolved with NA-2 is mixed with it, carry out suction filtration stir 1～5h at 5～50 DEG C after dry.
Further scheme is: the step (4) in above-mentioned preparation method, and described organic solvent is methyl alcohol or acetone, described catalyzer is Fe/HCl, Sn/HCl or load type metal Pd catalyst P d/C.
A further object of the present invention is to provide the application of described beta nucleater.
Described beta nucleater is for modified polypropene.
Further scheme is: in the time of modified polypropene, the consumption of beta nucleater used is 0.01～5% of polypropylene quality.
The present invention has the following advantages:
1. the beta nucleater selectivity and the nucleation efficiency that provided are high, carry out after blend with acrylic resin, can induce polypropylene to produce the β crystalline substance of high-content, can improve largely polyacrylic Tc simultaneously.After having added massfraction be 0.1% this beta nucleater in polypropylene, with respect to un-added polypropylene material, its Tc can improve 10 DEG C of left and right, and beta crystal content is up to 94%.For polypropylene pure sample, its Tc and beta crystal content have had and have significantly improved.
2. with other beta nucleaters, as application, wider commercial rare earth class nucleator WBG compares with amides nucleator TMB, the amides polypropylene beta nucleator providing, N, N '-dicyclohexyl-1,5-diamino-2,6-aphthalimide, have higher selectivity and nucleation efficiency, when same amount, induction produces more β crystalline substance.
3. in the beta nucleater structure that provided with have reactive behavior-NH
2functional group, can carry out some with other materials and specifically react, and further expands the function of this beta nucleater.
Embodiment
Embodiment 1
For convenience of description, preparation N, N '-dicyclohexyl-1,5-diamino-2, the intermediate product that the process of 6-aphthalimide (NA) relates to is used respectively NA-1, and NA-2 and NA-3 represent.
It should be noted that simultaneously, the present embodiment is only won the some concrete numerical parameter in listed scope in specification sheets and is set forth, those skilled in the art can know, as long as within listed scope, all can complete concrete preparation process of the present invention in specification sheets.
First be the synthetic of NA-1: to the dense HNO of 100ml90%
3in slowly add 10.5g2,2-naphthalene dicarboxylic acids, and at room temperature placing two hours, then mixed solution is heated to 60 DEG C, stirs 12h.Finally mixed solution is poured in frozen water and pressed powder that suction filtration is drying to obtain 6.67g white is NA-1, productive rate is 45%.Its reaction formula is:
Next is the synthetic of NA-2: 1.78g NA-1 is dissolved in to 18mL1, in 2-ethylene dichloride, and adds 0.03g catalyzer benzyltriethylammoinium chloride.Mixed solution heating, then adds 1.55g sulfur oxychloride (SOCl
2) make after mixed-liquor return 12h coolingly, obtaining 1.04g yellow solid by ether filtering and washing and be NA-2, productive rate is 83%.Its reaction formula is:
Then be the synthetic of NA-3: 1.45g hexahydroaniline is joined to 30ml methylene dichloride (CH
2cl
2) in, be dissolved with 30ml triethylamine (Et simultaneously
3n).Then the 10mL CH of 2.4g NA-2 will be dissolved with
2cl
2in the mixed solution of solution before joining, at room temperature stir 1h, obtain 2.87g white solid and be NA-3 subsequently by dry throw out suction filtration, productive rate is 87.5%.Its reaction formula is:
The synthetic of NA further: in the 50mLMeOH solution that contains 4.1g NA-3, add 1.23g Pd/C catalyzer, mixed solution stirs 12h at 40 DEG C, then 500mL dimethyl sulfoxide (DMSO) (DMSO) filtering and washing for mixed solution, finally obtain the tan solid of 2.4g and be NA, productive rate is 68%.Its reaction formula is:
Finally using the product NA obtaining as beta nucleater and dried polypropylene (density is 0.92g/cm for trade mark T30S, melt flow rate (MFR) 2.3g/10min
3) carry out blend banburying in the ratio of massfraction 0.05%:99.95% at torque rheometer XSS-300, experimental temperature is 200 DEG C, and rotating speed is 50r/min, and the time is 5min, obtains the polypropylene sample containing beta nucleater NA.Get 5～10mg and carry out DSC test on differential scanning calorimeter TA Q20, survey its Tc, result is as shown in table 1; Get in addition the polypropylene sample that appropriate torque obtains and under accurate automatic tableting press, be pressed into the thin slice that is about 0.5mm, use X-ray diffractometer X ' Pert Pro MPD DY1291 to carry out XRD test, survey its beta crystal content K
β, test result is as shown in table 1.
Embodiment 2
Be 0.1%:99.9% by the beta nucleater that in embodiment 1 prepared by same procedure with polyacrylic massfraction ratio, other processing conditionss and program are all constant, survey its Tc and beta crystal content, and result is as shown in table 1.
Embodiment 3
Be 0.3%:99.7% by the beta nucleater that in embodiment 1 prepared by same procedure with polyacrylic massfraction ratio, other processing conditionss and program are all constant, survey its Tc and beta crystal content, and result is as shown in table 1.
Embodiment 4
Be 0.5%:99.5% by the beta nucleater that in embodiment 1 prepared by same procedure with polyacrylic massfraction ratio, other processing conditionss and program are all constant, survey its Tc and beta crystal content, and result is as shown in table 1.
For understanding the synthetic polypropylene beta nucleant agent N preparing of the present invention, N '-dicyclohexyl-1,5-diamino-2, the feature of 6-aphthalimide concrete application in polypropylene material, get respectively two kinds of widely used efficient polypropylene beta nucleators (commercial rare earth class nucleator WBG-II, Guangdong Weilinna Function Materials Co., Ltd's production; Commercial amides nucleator TMB, Shanxi chemical institute is produced) compare, other processing conditionss and program be with embodiment 1, and comparative example a1, a2, a3 and a4 respectively corresponding WBG-II massfraction are 0.05%, 0.1%, 0.3% and 0.5% polypropylene sample; B1, b2, b3 and b4 respectively corresponding TMB massfraction are 0.05%, 0.1%, 0.3% and 0.5% polypropylene sample.In addition, according to same work program, pure polypropylene T30S is carried out to above-mentioned test as reference.
The Tc data of the each test specimens of table 1
Note: the relative content K of beta crystal in sample
βadopt Turner-Jones formula to calculate.
As can be seen from Table 1, in the situation that beta nucleater content is identical, obtain with the present invention beta nucleating agent modified polypropylene after, in sample, beta crystal content and Tc are higher, be the present invention obtain the selectivity of beta nucleater and nucleation efficiency high compare other two kinds commercial beta nucleater WBG-II and TMB higher, be a kind of polypropylene beta nucleator of excellence.
Claims (7)
1. a polypropylene beta nucleator, is characterized in that the structural formula of described polypropylene beta nucleator is:
2. the preparation method of polypropylene beta nucleator described in claim 1, is characterized in that, comprises the following steps:
(1) in 100～300ml acid with strong oxidizing property, add 10～30g naphthalene dicarboxylic acids, by mixed solution heated and stirred, controlling temperature of reaction is 50～100 DEG C, reaction times 10～24h, afterwards reaction solution is carried out that suction filtration is dry obtains intermediate product NA-1, NA-1 structural formula is:
(2) 1～5g NA-1 is dissolved in 10～30ml organic solvent, add the catalyzer of 0～0.1g, then the acyl chlorides agent sulfur oxychloride that to add with NA-1 mol ratio be 1:1～5:1, controlling temperature of reaction is 50～100 DEG C, reaction times 10～24h, obtain intermediate product NA-2 to reaction solution suction filtration is dry afterwards, NA-2 structural formula is:
(3) hexahydroaniline that is 1:1～3:1 by mol ratio and triethylamine join in 10～50ml organic solvent, then 5～20ml the dichloromethane solution that is dissolved with 1～5gNA-2 is mixed with it, at 5～50 DEG C, stir 1～5h, afterwards the dry intermediate product obtaining of reaction solution suction filtration is to NA-3, NA-3 structural formula is:
(4) after adding the catalyzer of 0.5～1.5g in the 50ml organic solution that contains 1～5g NA-3, at 20～50 DEG C, stir 10～24h, mixed solution is dry by 300～500ml dimethyl sulfoxide (DMSO) filtering and washing again, finally obtains tan solid and is target product polypropylene beta nucleator;
In step (1), acid with strong oxidizing property is concentrated nitric acid, and before suction filtration, reaction solution need to dilute in frozen water.
3. the preparation method of polypropylene beta nucleator according to claim 2, is characterized in that: in step (2), organic solvent used is 1,2-ethylene dichloride, catalyzer used is pyridine, dimethyl formamide DMF or benzyltriethylammoinium chloride.
4. the preparation method of polypropylene beta nucleator according to claim 2, is characterized in that: in step (3), organic solvent used is methylene dichloride.
5. the preparation method of polypropylene beta nucleator according to claim 2, is characterized in that: in step (4), organic solvent used is methyl alcohol or acetone, catalyzer used is Fe/HCl, Sn/HCl or load type metal Pd catalyst P d/C.
6. the application of polypropylene beta nucleator in modified polypropene described in claim 1.
7. the application of polypropylene beta nucleator in modified polypropene according to claim 6, the consumption that it is characterized in that polypropylene beta nucleator is 0.01～5% of polypropylene quality.
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| CN102731832B (en) * | 2012-07-05 | 2013-11-06 | 四川大学 | Graphene-loaded beta nucleating agent, preparation method and application thereof |
| CN102875900B (en) * | 2012-10-17 | 2014-04-02 | 四川大学 | Preparation method capable of toughening and reinforcing polypropylene product |
| CN109535561B (en) * | 2018-12-03 | 2020-06-30 | 四川大学 | Polypropylene β nucleating agent microcrystal and preparation method and application thereof |
| CN109776613A (en) * | 2019-01-15 | 2019-05-21 | 顺德职业技术学院 | Three phosphonitrile fire retardant of ring and its synthetic method with β crystalline substance induction nucleation |
| CN114350062B (en) * | 2021-12-08 | 2023-05-02 | 界首市天鸿新材料股份有限公司 | High-rigidity low-yield polypropylene torsion film and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6235823B1 (en) * | 1992-01-24 | 2001-05-22 | New Japan Chemical Co., Ltd. | Crystalline polypropylene resin composition and amide compounds |
| CN102040532A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Preparation method of polypropylene beta crystalline nucleating agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6235823B1 (en) * | 1992-01-24 | 2001-05-22 | New Japan Chemical Co., Ltd. | Crystalline polypropylene resin composition and amide compounds |
| CN102040532A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Preparation method of polypropylene beta crystalline nucleating agent |
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