CN105131334A - Preparation and application of composite polypropylene nucleating agent containing aromatic heterocyclic phosphate - Google Patents
Preparation and application of composite polypropylene nucleating agent containing aromatic heterocyclic phosphate Download PDFInfo
- Publication number
- CN105131334A CN105131334A CN201510656372.4A CN201510656372A CN105131334A CN 105131334 A CN105131334 A CN 105131334A CN 201510656372 A CN201510656372 A CN 201510656372A CN 105131334 A CN105131334 A CN 105131334A
- Authority
- CN
- China
- Prior art keywords
- nucleating agent
- formula
- polypropylene
- methylene
- category
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a synthesis method for a polypropylene nucleating agent. The polypropylene nucleating agent has an improvement effect on mechanical, optical and crystallization properties of polypropylene. The composite nucleating agent contains an A-type compound expressed by the formula (I) and/or the formula (II) and a B-type compound with inorganic salt and/or organic salt being the body. In the formula (I), R1, R2, R3 and R4 represent hydrogen atoms or alkyl groups; in the formula (II), R5, R6, R7 and R8 represent alkyl groups, M represents alkali metal positive ions, and n=1, 2, 3; the inorganic salt and/or organic salt contains lithium carbonate, hydrotalcite, sodium benzoate, lithium stearate, sodium stearate, zinc stearate, calcium stearate and others. The composite nucleating agent can obviously improve the rigidity, tenacity and crystallization performance of polypropylene.
Description
Technical field
The present invention relates to a kind of additive of acrylic resin, specifically, relate to a kind of composite nucleating agent of the acrylic resin containing substituted aromatic heterocyclic phosphate; Belong to technical field of novel materials.
Background technology
Polypropylene (PP) is all widely used in automotive industry, household electrical appliance, electronics and building materials furniture etc.But it has, and the transparency is poor, shrinking percentage large, and creep resistance is poor, the shortcomings such as fast light, hot and ageing resistance is poor, by adding organic molecule nucleator regulation and control PP crystallisation process, microtexture and form, can improve macroscopical application performance of PP effectively.At present, two kinds of nucleators that PP nucleation modification consumption is maximum are diphenylmethylene glucitols and substituted aryl heterocycle phosphate compounds.With regard to mist degree, the effect of substituted aryl heterocycle phosphoric acid ester nucleant agent N A11, NA21 a little less than Sorbitol Nucleator DM, 3988, but then has obvious advantage for improving PP mechanical property such as tensile strength and modulus in flexure substituted aryl heterocycle phosphate compounds.In addition, Sorbitol Nucleator is unstable under there is processing high temperature, easily decomposes and discharges parent aldehyde material, thus produce the shortcoming of smell, be not suitable for and food product pack, container.Substituted aryl heterocycle phosphoric acid ester nucleator has Heat stability is good compared to Sorbitol Nucleator, the use temperature upper limit can reach 400 DEG C, add the feature of free from extraneous odour in man-hour, a few money nucleators have wherein obtained U.S. FDA accreditation all, worldwide can be used in the packaging vessel with Food Contact.Therefore, from expansion PP Application Areas this respect, substituted aryl heterocycle phosphoric acid ester nucleator occupies obvious advantage.
For a kind of nucleator determined, add identical massfraction, become the quantity of nuclear particle more, nucleation efficiencies is higher.The quantity of particle depends on size and the distribution of nucleator.Substituted aryl heterocycle phosphoric acid ester nucleator is insoluble under polyacrylic processing temperature not to be melted, and the polarity of its molecule is comparatively large, and poor with polyacrylic consistency, the dispersiveness in polypropylene is also poor, thus have impact on its nucleation efficiencies.Therefore, the performance that the dispersiveness of this type of nucleator in PP improves nucleation efficiencies by being conducive to and finally improve PP is improved.By changing the size of nucleator, to improve its dispersiveness in PP be the most direct method, but nano level nucleator is easily reunited, and adding of nanoparticle often promotes that PP generates a small amount of β crystalline substance, cause goods to turn white, destroy the transparency of PP.
We find that substituted aryl heterocycle phosphate ester salt (as substituted aryl heterocycle phosphalugel) melting or the mineral compound (as sodium stearate) be dissolved in PP melt ion exchange reaction can occur with another kind of in the course of processing in the PP course of processing, generate a kind of substituted aryl heterocycle phosphate metal salt.Experimental result shows, when these two kinds of materials add PP processing simultaneously, all have synergistic effect, and its nucleating effect to be better than the substituted aryl heterocycle phosphate metal salt nucleator adding separately identical amount to the optical property of PP, mechanical property, crystal property.We infer that its reason is this compound under PP processing temperature in molten state, can be dispersed in well in PP melt, and the nucleator that two kinds of compounds are generated by ion exchange reaction can be dispersed in PP melt better.Further, because the place of reaction product generation is in PP melt, is subject to the effect of Strong shear, can effectively avoids reuniting between newly-generated nucleator.This improves the dispersiveness of nucleator, and then improve the performance of its modified PP.
Summary of the invention
For solving above shortcomings part in existing polypropylene nucleater technology, the object of the present invention is to provide a kind of preparation method of binary composite polypropylene nucleator and the application of nucleator prepared therefrom.The method containing substituted aromatic heterocyclic phosphate and inorganic salt and/or organic salt composite is adopted to prepare polypropylene nucleater, having that consumption is few, price is low, preparation technology is simple, improve the advantages such as mechanical property, is a kind of desirable mechanics properties-correcting agent with the acrylic resin of synergistic effect.
The object of this invention is to provide a kind of preparation method of binary composite polypropylene nucleator.
Described method comprises:
Described nucleator is that substituted aromatic heterocyclic phosphate and machine salt and/or organic salt are composite obtained;
Wherein, the weight ratio of substituted aromatic heterocyclic phosphate and inorganic salt and/or organic salt is 95:5-5:95;
Described substituted aromatic heterocyclic phosphate is the compound that formula (I) and/or formula (II) represent.R in formula (I)
1, R
2, R
3and R
4identical or not identical, represent hydrogen atom or alkyl respectively; R in formula (II)
5, R
6, R
7and R
8identical or not identical, represent hydrogen atom or C respectively
1-C
6the alkyl of substituted or unsubstituted straight or branched, M represents alkali metal cation, n=1,2,3;
Described inorganic salt and/or organic salt are one or more in Quilonum Retard, hydrotalcite, Sodium Benzoate, lithium stearate, sodium stearate, Zinic stearas, calcium stearate etc.;
The using method of described composite nucleating agent be composite after be mixed in polypropylene granules, in high-speed mixer, mix about 5min, then extruding pelletization in twin screw extruder;
The invention provides the application of a kind of binary composite polypropylene nucleator in preparation Reinforced Polypropylene.
Compared with prior art, advantage of the present invention is as follows:
1, the inorganic salt part in polypropylene composite materials nucleator of the present invention is molten state under polypropylene processing temperature, can be dispersed in melt polypropylene well, the nucleator that two kinds of compounds are generated by ion exchange reaction can be dispersed in melt polypropylene better, and then improves its final effect;
2, polypropylene composite materials nucleator of the present invention is as the nucleus of crystalline polymer, while promoting the growth of crystallization, refinement crystalline size, has good nucleating effect and crystallization velocity faster;
3, polypropylene composite materials nucleator of the present invention has the advantages such as consumption is few, effective, tooling cost is low, preparation technology is simple, is a kind of mechanics properties-correcting agent of desirable acrylic resin;
4, the present invention obtains the composite nucleating agent with synergy, and while the crystal property of material and mechanical property improve, cost declines to a great extent.
Accompanying drawing explanation
Fig. 1 is the substituted aromatic heterocyclic phosphate chemical formula schematic diagram that the present invention adopts;
Wherein, R in formula (I)
1, R
2, R
3and R
4identical or not identical, represent hydrogen atom or alkyl respectively; R in formula (II)
5, R
6, R
7and R
8identical or not identical, represent hydrogen atom or C respectively
1-C
6the alkyl of substituted or unsubstituted straight or branched, M represents alkali metal cation, n=1,2,3.
Claims (12)
1. a nucleating agent compositions, this nucleating agent compositions contains the category-B compound that the category-A compound and inorganic salt that are represented by formula (I) and/or formula (II) and/or organic salt are main body, R in formula (I)
1, R
2, R
3and R
4identical or not identical, represent hydrogen atom or alkyl respectively; R in formula (II)
5, R
6, R
7and R
8identical or not identical, represent hydrogen atom or C respectively
1-C
6the alkyl of substituted or unsubstituted straight or branched, M represents alkali metal cation, n=1,2,3; Inorganic salt have Quilonum Retard, hydrotalcite etc.; Organic salt has Sodium Benzoate, lithium stearate, sodium stearate, Zinic stearas, calcium stearate etc.
2. nucleating agent compositions according to claim 1, wherein, with the total mass of composition for benchmark, described category-A compound accounts for 5-95 % by weight, and described category-B compound accounts for 95-5 % by weight.
3. nucleator constituent according to claim 1, wherein, formula (I) and the middle metallic cation representated by M of formula (II) are the one in the metallic cations such as Li, Na, Mg, Al, K, Ca, Zn, Ba, Ti.
4. nucleating agent compositions according to claim 3, wherein said category-A compound is one or more in following compounds: 2, 2 '-methylene-bis (4, 6-di-t-butyl phenoxy group) phosphoric acid ester, 2, 2 '-methylene-bis (4, 6-di-t-butyl phenoxy group) Trilithium phosphate, 2, 2 '-methylene-bis (4, 6-di-t-butyl phenoxy group) sodium phosphate, 2, 2 '-methylene-bis (4, 6-di-t-butyl phenoxy group) potassiumphosphate, 2, 2 '-methylene-bis (4, 6-di-t-butyl phenoxy group) trimagnesium phosphate, 2, 2 '-methylene-bis (4, 6-di-t-butyl phenoxy group) calcium phosphate, 2, 2 '-methylene-bis (4, 6-di-t-butyl phenoxy group) zinc phosphate, 2, 2 '-methylene-bis (4, 6-di-t-butyl phenoxy group) barium phosphate, 2, 2 '-methylene-bis (4, 6-di-t-butyl phenoxy group) phosphoric acid ester oxyaluminum salt etc.
5. nucleating agent compositions according to claim 1, wherein, described category-B compound is one or more in following inorganic salt and/or organic salt: Quilonum Retard, hydrotalcite, Sodium Benzoate, lithium stearate, sodium stearate, Zinic stearas, calcium stearate etc.
6. nucleating agent compositions according to claim 3, the raw materials of wherein said category-A compound reacts preparation after dissolving completely in a solvent.
7. method according to claim 6, wherein reaction solvent is one or more the mixture in following material: acetone, methyl alcohol, ethanol, propyl alcohol, butanols, ethyl acetate, benzene, toluene, tetrahydrofuran (THF), hexanaphthene, normal hexane etc.
8. the preparation method of a nucleating agent compositions, the method comprises the steps: that category-A compound and category-B inorganic salt and/or organic salt ion exchange reaction occur extruding in the process of processing with polypropylene, generate the substituted aryl heterocycle phosphate ester salt with better nucleating effect, effectively can avoid the reunion of substituted aryl heterocycle phosphate ester salt simultaneously, make it be dispersed in uniformly in melt polypropylene.
9. method according to claim 7, wherein, in mixed solvent, the content of two kinds of solvents is 10-90 % by weight.
10. method according to claim 6, wherein, the reaction conditions of described category-A compound comprises: temperature is 10-90 DEG C, and the time is 0.1-10 hour.
11. 1 kinds of polypropylene materials, this polypropylene contains acrylic resin and nucleating agent compositions, it is characterized in that, described nucleating agent compositions is the nucleating agent compositions in claim 1-5 described in any one.
12. polypropylene materials according to claim 11, wherein, relative to the acrylic resin of 100 weight parts, the content of nucleator is 0.01-1 weight part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510656372.4A CN105131334A (en) | 2015-10-12 | 2015-10-12 | Preparation and application of composite polypropylene nucleating agent containing aromatic heterocyclic phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510656372.4A CN105131334A (en) | 2015-10-12 | 2015-10-12 | Preparation and application of composite polypropylene nucleating agent containing aromatic heterocyclic phosphate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105131334A true CN105131334A (en) | 2015-12-09 |
Family
ID=54716937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510656372.4A Pending CN105131334A (en) | 2015-10-12 | 2015-10-12 | Preparation and application of composite polypropylene nucleating agent containing aromatic heterocyclic phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105131334A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105633328B (en) * | 2016-01-06 | 2018-12-28 | 河南师范大学 | Lithium ion battery polypropylene porous septum and preparation method thereof |
| CN110615916A (en) * | 2018-06-20 | 2019-12-27 | 华东理工大学 | Composite polypropylene nucleating agent and preparation method and application thereof |
| CN110615915A (en) * | 2018-06-20 | 2019-12-27 | 华东理工大学 | Composite polypropylene nucleating agent and preparation method and application thereof |
| CN111234314A (en) * | 2020-04-01 | 2020-06-05 | 山西省化工研究所（有限公司） | Complex nucleating agent for polyester and preparation method thereof |
| CN111378207A (en) * | 2020-04-01 | 2020-07-07 | 山西省化工研究所（有限公司） | Nucleating agent for polyolefin |
| CN111712539A (en) * | 2018-02-13 | 2020-09-25 | 株式会社Adeka | Nucleating agent, polyolefin resin composition using same, and molded article 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 |
| EP3831874A4 (en) * | 2018-07-27 | 2022-04-27 | Adeka Corporation | Additive composition, polyolefin resin composition containing same, method for producing polyolefin resin composition, and molded articles thereof |
| CN114409962A (en) * | 2022-01-07 | 2022-04-29 | 北京吉海川科技发展有限公司 | Treatment method and application of nucleating agent |
-
2015
- 2015-10-12 CN CN201510656372.4A patent/CN105131334A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105633328B (en) * | 2016-01-06 | 2018-12-28 | 河南师范大学 | Lithium ion battery polypropylene porous septum and preparation method thereof |
| CN111712539A (en) * | 2018-02-13 | 2020-09-25 | 株式会社Adeka | Nucleating agent, polyolefin resin composition using same, and molded article thereof |
| US11306194B2 (en) | 2018-02-13 | 2022-04-19 | Adeka Corporation | Nucleating agent, polyolefin-based resin composition containing same, and molded article thereof |
| CN110615916A (en) * | 2018-06-20 | 2019-12-27 | 华东理工大学 | Composite polypropylene nucleating agent and preparation method and application thereof |
| CN110615915A (en) * | 2018-06-20 | 2019-12-27 | 华东理工大学 | Composite polypropylene nucleating agent and preparation method and application thereof |
| EP3831874A4 (en) * | 2018-07-27 | 2022-04-27 | Adeka Corporation | Additive composition, polyolefin resin composition containing same, method for producing polyolefin resin composition, and molded articles thereof |
| US11795300B2 (en) | 2018-07-27 | 2023-10-24 | Adeka Corporation | Additive composition, polyolefin resin composition containing same, method for producing polyolefin resin composition, and molded articles 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 |
| CN111234314A (en) * | 2020-04-01 | 2020-06-05 | 山西省化工研究所（有限公司） | Complex nucleating agent for polyester and preparation method thereof |
| CN111378207A (en) * | 2020-04-01 | 2020-07-07 | 山西省化工研究所（有限公司） | Nucleating agent for polyolefin |
| CN114409962A (en) * | 2022-01-07 | 2022-04-29 | 北京吉海川科技发展有限公司 | Treatment method and application of nucleating agent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105131334A (en) | Preparation and application of composite polypropylene nucleating agent containing aromatic heterocyclic phosphate | |
| CN103030886B (en) | Transparent polypropylene and preparing method thereof | |
| CN107849339B (en) | The manufacturing method of polybutylene terephthalate (PBT) resin combination and the manufacturing method of polybutylene terephthalate (PBT) resin-formed body | |
| CN103073862A (en) | Halogen-free flame-retardant polylactic acid nanocomposite and preparation method thereof | |
| CN101265347B (en) | Polypropylene transparent nucleater | |
| CN104114616A (en) | Resin additive master batch | |
| CN102492236A (en) | Novel high-efficiency calcium-zinc stabilizer applied for PVC (polyvinyl chloride) section bars and preparation method thereof | |
| CN101070363B (en) | Process for preparing transparent polypropylene | |
| US6642290B1 (en) | Highly nucleated syndiotactic polypropylene | |
| CN107383584A (en) | A kind of high just high mould thin-walled injection moulding polypropylene material and preparation method thereof | |
| JP2013133364A (en) | Additive composition for biodegradable resin | |
| CN102408626A (en) | Polypropylene anti-reflection nucleating agent and preparation method thereof | |
| CN104974377A (en) | Nucleating agent composition containing cyclic carboxylic acid metal salt | |
| CN105061404A (en) | Imide polypropylene beta crystalline form nucleating agent and preparation method thereof | |
| CN104151723A (en) | Filled polybutylene composite material used in fast-forming parts, and preparation method thereof | |
| EP1044968B1 (en) | 6-Amino-2-oxo-pyrimidin-4-one derivatives, their preparation and their use as stabilisers for halogen-containing polymers | |
| JP6908892B2 (en) | Polyamide resin composition containing a metal salt of a phenylphosphonic acid compound | |
| CN106084446A (en) | A kind of enhancing PP/ABS alloy material and preparation method thereof | |
| US6703434B2 (en) | Methods of producing highly nucleated syndiotactic polypropylene | |
| CN102807685B (en) | Organic phosphate nucleating agent composition and preparation method thereof and polypropylene material | |
| CN104558847A (en) | Homo-polypropylene beta nucleating agent and preparation method thereof | |
| WO2003087175A1 (en) | Highly nucleated syndiotactic polypropylene | |
| JP6005349B2 (en) | Polyamide resin composition | |
| CN104693724A (en) | PC/PET alloy with excellent aging resistance | |
| CN106519423A (en) | Transparent polypropylene material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20151209 |