CN102344388A - 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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- CN102344388A CN102344388A CN2011102015991A CN201110201599A CN102344388A CN 102344388 A CN102344388 A CN 102344388A CN 2011102015991 A CN2011102015991 A CN 2011102015991A CN 201110201599 A CN201110201599 A CN 201110201599A CN 102344388 A CN102344388 A CN 102344388A
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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 the preparation method and the application of said beta nucleater.
Background technology
Vestolen PP 7052 (PP) is one of five big general-purpose plastics, has good processing, mechanics and chemical resistance, has at aspects such as household electrical appliance, automobile, electronics, packing and building materials furniture widely to use.But PP also has many weak points, particularly poor toughness, and low temperature brittleness is big, has limited the further expansion of PP Application Areas.Therefore, PP is carried out modification and have important significance for theories and wide commercial space.Vestolen PP 7052 is a kind of heteromorphic polymer, has crystal formations such as α, β, γ, δ and plan hexagonal crystal, and wherein beta crystal density is lower; Short texture; Receive external force to be easy to generate viscous deformation, form little crazing or micropore, thereby help the toughness that dissipation of energy improves PP as the time spent.Therefore, in the molding process of PP, manage to induce the brilliant generation of a large amount of β in the system, can reach the purpose of Toughened PP.
Beta nucleater is to induce PP to produce one type of brilliant material of high-content β.Beta nucleater is divided into organic and inorganic two big types.Organic class mainly contains condensed-nuclei aromatics class (dye class), amides, organic acid and salt.Mineral-type mainly contains inorganic salts, inorganic oxide and some low melting point metal powder.The beta nucleater that is used for commercialization production the earliest is the aromatic amine nucleator.This type of beta nucleater is applied for a patent in 1992 by Japan new physics and chemistry company, and has realized commercialization in 1998.Common aromatic amine nucleator mainly contains two kinds: 2, and 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, China Shanxi chemical research institute develops the beta nucleater that trade names are TMB-4 and TMB-5, is substituted aromatic amide, also belongs to this type of.CN 85100465 and CN 101605749A etc. disclose a series of (particularly pimelic acid and calcium stearate) beta nucleaters of being made up of the salt of IIA family metallic element in di-carboxylic acid and the periodictable.CN 00117339 discloses rare earth organic complex WBG as the polypropylene beta nucleator.
In order to reduce cost and to improve the nucleation efficient of beta nucleater, CN 101157771B and CN 101580601A disclose at first di-carboxylic acid have been carried out load, and then prepare the method for beta nucleater.CN 101619143B discloses a kind of fiber-loaded beta nucleating agent, and the excellent toughness that the enhancement function of filamentary material capable of using and β are brilliant, the PP composite material that makes preparation obviously improve the toughness and the ductility of material when intensity and modulus do not reduce.Above-mentioned loading type beta nucleater all is the expanded application about the beta nucleater of organic acid and salt.For other type beta nucleater, but owing to lack the reactive activity group on its structure, its further modification is used and 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 efficient.
Beta nucleater of the present invention is N, N '-dicyclohexyl-1,5-diamino--2,6-aphthalimide.Its structural formula is following:
This beta nucleater can improve the Vestolen PP 7052 beta crystal content, improves the crystalling propylene temperature, thereby reaches the purpose of improving Properties of Polypropylene.Have on its structure simultaneously have reactive behavior-NH
2Functional group can carry out some specific reaction with other materials, further expands the function of this beta nucleater.
Another object of the present invention provides the preparation method of said beta nucleater.
The preparation method of beta nucleater provided by the invention is following:
(1) in 100～300ml acid with strong oxidizing property, add 10～30g naphthalene dicarboxylic acids, with the mixed solution heated and stirred, control reaction temperature is 50～100 ℃, and reaction times 10～24h carries out the suction filtration drying to reaction solution afterwards and obtains intermediate product NA-1;
(2) 1～5g NA-1 is dissolved in 10～30ml organic solvent; The catalyzer that adds 0～0.1g; Adding and NA-1 mol ratio are 1: 1～5: 1 acyl chlorides agent sulfur oxychloride then; Control reaction temperature is 50～100 ℃, and reaction times 10～24h obtains intermediate product NA-2 to reaction solution suction filtration drying afterwards;
(3) be that 1: 1～3: 1 hexahydroaniline and triethylamine joins in 10～50ml organic solvent with mol ratio; 1～5g NA-2 is dissolved in forms 5～20ml solution in the identical organic solvent; These two kinds of solution are mixed; Stir 1～5h down at 5～50 ℃, the intermediate product that afterwards reaction solution suction filtration drying is obtained is NA-3;
(4) stir 10～24h down at 20～50 ℃ after will containing the catalyzer that adds 0.5～1.5g in the 50ml organic solution of 1～5g NA-3; Mixed solution uses 300～500ml DMSO 99.8MIN. filtering and washing dry again; Obtain tan solid at last and be title product NA, be i.e. the polypropylene beta nucleator.
Scheme further is: the step among the above-mentioned preparation method (1), described acid with strong oxidizing property is a concentrated nitric acid, and reaction solution need dilute in frozen water before the suction filtration.
Scheme further is: the step among the above-mentioned preparation method (2), described organic solvent are 1, and 2-ethylene dichloride, described catalyzer are pyridine, N DMF or benzyltriethylammoinium chloride.
Scheme further is: the step among the above-mentioned preparation method (3); Described organic solvent is a methylene dichloride; And hexahydroaniline and triethylamine are joined in an amount of methylene dichloride, and the dichloromethane solution that will be dissolved with NA-2 then mixes with it, carries out the suction filtration drying behind stirring 1～5h down at 5～50 ℃.
Scheme further is: the step among the above-mentioned preparation method (4), described organic solvent are methyl alcohol or acetone, and described catalyzer is Fe/HCl, Sn/HCl or load type metal Pd catalyst P d/C.
A purpose more of the present invention provides the application of said beta nucleater.
Said beta nucleater is used for modified polypropene.
Scheme further is: when modified polypropene, the consumption of used beta nucleater is 0.01～5% of a Vestolen PP 7052 quality.
The present invention has the following advantages:
1. the beta nucleater selectivity that is provided and nucleation efficient are high, carry out blend with acrylic resin after, it is brilliant to induce Vestolen PP 7052 to produce high-load β, can improve polyacrylic Tc largely simultaneously.After in Vestolen PP 7052, having added massfraction and being 0.1% this beta nucleater, with respect to un-added polypropylene material, its Tc can improve about 10 ℃, and beta crystal content is up to 94%.For the Vestolen PP 7052 pure sample, its Tc and beta crystal content have had and have significantly improved.
2. with other beta nucleaters, compare the amides polypropylene beta nucleator that is provided with amides nucleator TMB as using wider commercial rare earth class nucleator WBG; N; N '-dicyclohexyl-1,5-diamino--2,6-aphthalimide; Have higher selectivity and nucleation efficient, induce during same amount to produce more β crystalline substance.
3. have on the beta nucleater structure that is provided have reactive behavior-NH
2Functional group can carry out some specific reaction with other materials, 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 NA-1 respectively, and NA-2 and NA-3 represent.
Need to prove simultaneously; The some concrete numerical parameter that present embodiment is only won in the listed scope in the specification sheets is set forth; Those skilled in the art can know, as long as in specification sheets, within the listed scope, all can accomplish concrete preparation process of the present invention.
At first be the synthetic of NA-1: to the dense HNO of 100ml 90%
3In slowly add 10.5g 2,2-naphthalene dicarboxylic acids, and at room temperature placing two hours, mixed solution is heated to 60 ℃ then, stirs 12h.At last mixed solution is poured in the frozen water and suction filtration is drying to obtain 6.67g
Next is the synthetic of NA-2: 1.78g NA-2 is dissolved in 18mL 1; In the 2-ethylene dichloride, and add 0.03g catalysis
Be the synthetic of NA-3 then: the 1.45g hexahydroaniline is joined 30ml methylene dichloride (CH
2Cl
2) in, be dissolved with 30ml triethylamine (Et simultaneously
3N).To be dissolved with the 10mL CH of 2.4g NA-3 then
2Cl
2In the mixed solution before solution joins, at room temperature stir 1h, subsequently throw out suction filtration drying is obtained the 2.87g white solid and be NA-3, productive rate is 87.5%.Its reaction formula is:
Be the synthetic of NA further: in containing the 50mLMeOH solution of 4.1g NA-4, add 1.23g Pd/C catalyzer; Mixed solution stirs 12h down at 40 ℃; Mixed solution obtains the tan solid of 2.4g at last and is NA with 500mL DMSO 99.8MIN. (DMSO) filtering and washing then, and productive rate is 68%.Its reaction formula is:
At last with the product NA that obtains as beta nucleater and dried Vestolen PP 7052 (trade mark T30S, melt flow rate(MFR)
2.3g/10min density is 0.92g/cm
3) carry out the blend banburying in the ratio of massfraction 0.05%: 99.95% at torque rheometer XSS-300, experimental temperature is 200 ℃, and rotating speed is 50r/min, and the time is 5min, obtains containing the Vestolen PP 7052 sample of beta nucleater NA.Get 5～10mg and on DSC TA Q20, carry out the DSC test, survey its Tc, the result is as shown in table 1; Getting the Vestolen PP 7052 sample that an amount of torque obtains in addition is the thin slice of 0.5mm in the written treaty of accurate automatic tableting press pressed, uses X-ray diffractometer X ' Pert Pro MPD DY1291 to carry out the XRD test, surveys its beta crystal content K
β, test result is as shown in table 1.
Embodiment 2
Beta nucleater by same procedure preparation among the embodiment 1 is 0.1%: 99.9% with polyacrylic massfraction ratio, and other processing conditionss and program are all constant, survey its Tc and beta crystal content, and the result is as shown in table 1.
Embodiment 3
Beta nucleater by same procedure preparation among the embodiment 1 is 0.3%: 99.7% with polyacrylic massfraction ratio, and other processing conditionss and program are all constant, survey its Tc and beta crystal content, and the result is as shown in table 1.
Embodiment 4
Beta nucleater by same procedure preparation among the embodiment 1 is 0.5%: 99.5% with polyacrylic massfraction ratio, and other processing conditionss and program are all constant, survey its Tc and beta crystal content, and the result is as shown in table 1.
For understanding the synthetic polypropylene beta nucleator N for preparing of the present invention; N '-dicyclohexyl-1; 5-diamino--2; The 6-aphthalimide is the concrete characteristic of using in polypropylene material, gets two kinds of widely used efficient polypropylene beta nucleators (commercial rare earth class nucleator WBG-II, Guangdong Weilinna Function Materials Co., Ltd's production respectively; Commercial amides nucleator TMB; The Shanxi chemical institute is produced) contrast; Other processing conditionss and program are with embodiment 1, and the corresponding respectively WBG-II massfraction of Comparative Examples a1, a2, a3 and a4 is 0.05%, 0.1%, 0.3% and 0.5% Vestolen PP 7052 sample; The corresponding respectively TMB massfraction of b1, b2, b3 and b4 is 0.05%, 0.1%, 0.3% and 0.5% Vestolen PP 7052 sample.In addition, according to same work program pure Vestolen PP 7052 T30S is carried out above-mentioned test as reference.
The Tc data of each test specimens of table 1
Annotate: the relative content K of beta crystal in the sample
βAdopt the Turner-Jones formula to calculate.
Can find out from table 1; Under the identical situation of beta nucleater content; With the present invention obtain beta nucleater modified Vestolen PP 7052 after; Beta crystal content and Tc are higher in the sample, i.e. the present invention obtain compare other two kinds commercial beta nucleater WBG-II and TMB of selectivity and the nucleation efficient height of beta nucleater higher, be a kind of polypropylene beta nucleator of excellence.
Claims (8)
1. polypropylene beta nucleator is characterized in that the structural formula of said polypropylene beta nucleator is:
2. the preparation method of the said polypropylene beta nucleator of claim 1 is characterized in that, may further comprise the steps:
(1) in 100～300ml acid with strong oxidizing property, add 10～30g naphthalene dicarboxylic acids, with the mixed solution heated and stirred, control reaction temperature is 50～100 ℃, and reaction times 10～24h carries out the suction filtration drying to reaction solution afterwards and obtains intermediate product NA-1;
(2) 1～5g NA-1 is dissolved in 10～30ml organic solvent; The catalyzer that adds 0～0.1g; Adding and NA-1 mol ratio are 1: 1～5: 1 acyl chlorides agent sulfur oxychloride then; Control reaction temperature is 50～100 ℃, and reaction times 10～24h obtains intermediate product NA-2 to reaction solution suction filtration drying afterwards;
(3) be that 1: 1～3: 1 hexahydroaniline and triethylamine joins in 10～50ml organic solvent with mol ratio; 5～20ml dichloromethane solution that will be dissolved with 1～5gNA-2 then mixes with it; Stir 1～5h down at 5～50 ℃, the intermediate product that afterwards reaction solution suction filtration drying is obtained is NA-3;
(4) stir 10～24h down at 20～50 ℃ after will containing the catalyzer that adds 0.5～1.5g in the 50ml organic solution of 1～5g NA-3; Mixed solution uses 300～500ml DMSO 99.8MIN. filtering and washing dry again, obtains tan solid at last and is title product polypropylene beta nucleator.
3. according to the preparation method of the said polypropylene beta nucleator of claim 2, it is characterized in that: in the step (1), acid with strong oxidizing property is a concentrated nitric acid, and reaction solution need dilute in frozen water before the suction filtration.
4. according to the preparation method of the said polypropylene beta nucleator of claim 2, it is characterized in that: used organic solvent is 1 in the step (2), and 2-ethylene dichloride, used catalyzer are pyridine, N DMF or benzyltriethylammoinium chloride.
5. according to the preparation method of the said polypropylene beta nucleator of claim 2, it is characterized in that: used organic solvent is a methylene dichloride in the step (3).
6. according to the preparation method of the said polypropylene beta nucleator of claim 2, it is characterized in that: used organic solvent is methyl alcohol or acetone in the step (4), and used catalyzer is Fe/HCl, Sn/HCl or load type metal Pd catalyst P d/C.
7. the application of the said polypropylene beta nucleator of claim 1 in modified polypropene.
8. according to the application of the said polypropylene beta nucleator of claim 7 in modified polypropene, the consumption that it is characterized in that the polypropylene beta nucleator is 0.01～5% of a Vestolen PP 7052 quality.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731832A (en) * | 2012-07-05 | 2012-10-17 | 四川大学 | Graphene-loaded beta nucleating agent, preparation method and application thereof |
| CN102875900A (en) * | 2012-10-17 | 2013-01-16 | 四川大学 | Preparation method capable of toughening and reinforcing polypropylene product |
| CN109535561A (en) * | 2018-12-03 | 2019-03-29 | 四川大学 | Polypropylene beta nucleating agent crystallite and its preparation method and application |
| 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 |
| CN114350062A (en) * | 2021-12-08 | 2022-04-15 | 界首市天鸿新材料股份有限公司 | High-rigidity low-yield polypropylene tangle film and preparation method thereof |
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| 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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2011
- 2011-07-19 CN CN201110201599.1A patent/CN102344388B/en active Active
Patent 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 |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731832A (en) * | 2012-07-05 | 2012-10-17 | 四川大学 | Graphene-loaded beta nucleating agent, preparation method and application thereof |
| CN102731832B (en) * | 2012-07-05 | 2013-11-06 | 四川大学 | Graphene-loaded beta nucleating agent, preparation method and application thereof |
| CN102875900A (en) * | 2012-10-17 | 2013-01-16 | 四川大学 | Preparation method capable of toughening and reinforcing polypropylene product |
| CN102875900B (en) * | 2012-10-17 | 2014-04-02 | 四川大学 | Preparation method capable of toughening and reinforcing polypropylene product |
| CN109535561A (en) * | 2018-12-03 | 2019-03-29 | 四川大学 | Polypropylene beta nucleating agent crystallite and its preparation method and application |
| 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 |
| CN114350062A (en) * | 2021-12-08 | 2022-04-15 | 界首市天鸿新材料股份有限公司 | High-rigidity low-yield polypropylene tangle film and preparation method thereof |
| 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 |
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